TW201529511A - Treatment of a surface modification layer for controlled bonding of thin sheets with carriers - Google Patents

Abstract

A method of controllably bonding a thin sheet to a carrier, wherein the thin sheet has a thin sheet bonding surface, and the carrier has a carrier bonding surface. Depositing a surface modification layer onto at least one of the thin sheet bonding surface and the carrier bonding surface so as to obtain a first surface energy on the one of the thin sheet bonding surface and the carrier bonding surface. Then, treating the surface modification layer so as to change the first surface energy to a second surface energy, wherein the second surface energy is greater than the first. And bonding the thin sheet bonding surface to the carrier bonding surface via the surface modification layer. Depositing the surface modification layer, and treating it, may be done by plasma polymerization processes.

Description

Treatment of surface modification layers for controlled joining of sheets and carriers

The present application claims priority to U.S. Provisional Application Serial No. 61/931, 912, filed on Jan. 27, 2014, the disclosure of which is hereby incorporated by reference in its entirety.

The present invention relates to articles and methods for processing flexible sheets on a carrier, and more particularly to articles and methods for processing flexible glass sheets on glass carriers.

Flexible substrates offer the potential for a relatively inexpensive device that uses roll-to-roll processing, as well as the possibility of making thinner, lighter, more flexible, and durable displays. However, the techniques, equipment and processes required for roll-to-roll processing of high quality displays have not been fully developed. Since the panel manufacturer has invested heavily in the tool set for processing large glass sheets, it is provided that the flexible substrate is laminated to the carrier and processed by the sheet-to-sheet processing to provide a display device: A shorter-term solution to the value proposition of thin, lighter, and more flexible displays. Already in, for example, polyethylene naphthalate; A demonstration of a display on a polymer sheet of PEN) in which the fabrication of the device is made using a sheet of PEN laminated to a glass carrier to a sheet. The upper temperature limit of PEN limits the quality of the device and the process available. In addition, the high permeability of the polymer substrate results in environmental degradation of the OLED device, in which case near airtight packaging is required. Thin film encapsulation offers the prospect of overcoming such limitations, but it has not been proven to provide acceptable yields at large volumes.

In a similar manner, the display device can be fabricated using a glass carrier laminated to one or more thin glass substrates. It is expected that the low permeability of thin glass and improved temperature resistance and chemical resistance will allow for a higher performance, longer life flexible display.

However, thermal, vacuum, solvent and acid and ultra-flat Flat Panel Display (FPD) processes require a robust bond for the bonding of thin glass to the carrier. FPD processes typically involve vacuum deposition (sputtered metals, transparent conductive oxides and oxide semiconductors, chemical vapor deposition (CVD) deposition of amorphous germanium, tantalum nitride and hafnium, and metals and insulators). Dry etching), thermal process (including about 300-400 ° C CVD deposition, up to 600 ° C p-Si crystallization, 350-450 ° C oxide semiconductor annealing, up to 650 ° C dopant annealing, and about 200-350 ° C contact annealing ), acid etching (metal etching, oxide semiconductor etching), solvent exposure (stripping photoresist, deposition of polymer package), and ultrasonic exposure (in solvent stripping and aqueous cleaning of photoresists, typically) In an alkaline solution).

Adhesive wafer bonding has been widely used in micromechanical systems (MEMS) and semiconductor processing for back-end steps where processes are less demanding. Brewer Science And Henkel's commercial adhesives are typically thick polymer adhesive layers that are 5-200 microns thick. The large thickness of these layers causes a large amount of volatile components, trapped solvents and adsorbed substances to contaminate the FPD process. These materials thermally decompose and degas at temperatures above about 250 °C. Such materials may also cause contamination of downstream steps by acting as sinks for gases, solvents and acids, which may be degassed in subsequent processes.

Name February 8, 2012 to apply for Processing Flexible Glass with / No. 596,727 of 61 a Carrier of US Provisional Application Serial Number (hereinafter US'727) revealed that the concept involves the following: initially by Van der Waals force will For example, a sheet of flexible glass sheet is bonded to the carrier, and then the bonding strength in certain areas is increased while remaining on the processing sheet/carrier to form the device thereon (eg, an electronic or display device, an electronic or display device) The ability of a component, an organic light emitting device (OLED) material, a photo-voltaic (PV) structure, or a thin film transistor to remove portions of the wafer. At least a portion of the thin glass is bonded to the carrier such that the process process fluid is prevented from entering between the sheet and the carrier, thereby reducing the chance of contaminating the downstream process, i.e., the joint seal between the sheet and the carrier is airtight. And in some preferred embodiments, the seal surrounds the exterior of the article, thereby preventing liquid or gas from invading into or out of any area of the article of sealing.

US '727 continues to reveal that in low temperature polysilicon (LTPS) (which can be up to about 750 ° C compared to the low temperature of solid phase crystallization treatment), it can be used up to 600 ° C or greater. Temperature, vacuum and wet etching environments. These conditions limit the materials that can be used and place high demands on the carrier/sheet. Therefore, there is a need for a carrier method that utilizes the manufacturer's existing capital infrastructure to allow for the implementation of thin glass at higher processing temperatures (ie, having Treatment of a 0.3 mm thick glass) without contamination or loss of joint strength between the thin glass and the carrier, and wherein the thin glass is easily de-bonded to the carrier at the end of the process.

A commercial advantage of the method disclosed in US '727 is that, as indicated in US '727, manufacturers will be able to utilize their existing capital investment in processing equipment while obtaining thin glass sheets for use in, for example, PV, OLED, LCD. And the advantages of patterned Thin Film Transistor (TFT) electronic devices. In addition, the method allows for process flexibility, including: process flexibility for thin glass sheets and carriers cleaning and surface preparation to facilitate bonding; process flexibility for bonding between the sheet and the carrier at the joint area Process flexibility for maintaining the releasability of the self-carrier at the non-joined (or strength-reduced joint/low-strength joint) region; and process flexibility for cutting the flakes to facilitate extraction of the self-carrier.

In the glass to glass bonding process, the glass surface is cleaned to remove all metal, organic, and particulate residues, leaving a nearly sterol terminated surface. The glass surfaces are first brought into intimate contact, wherein the van der Waals and/or hydrogen bonding forces pull the surfaces together. The surface sterol groups condense to form a strong covalent Si-O-Si bond across the interface using heat and depending on the desired pressure to permanently fuse the glass block. Metals, organics, and particulate remnants will resist bonding by masking the surface, thereby preventing the intimate contact required for bonding. High sterol surface concentrations are also required to form strong bonds because the number of bonds per unit area will be determined by the probability of condensation of two sterol species on the opposite surface to synthesize water. Zhuravlel has reported that for fully hydrated cerium oxide, the average number of hydroxyl groups per nm ² is 4.6 to 4.9. Zhuravlel, LT, The Surface Chemistry of Amorphous Silika, Zhuravlev Model, Colloids and Surfaces A: Physiochemical Engineering Aspects 173 (2000) 1-38. In US '727, a non-joining zone is formed in the joint perimeter, and the primary way to form this non-joining zone is to increase the surface roughness. An average surface roughness greater than 2 nm Ra prevents the formation of glass to glass bonds during the high temperature of the bonding process. In the name and by the same inventors on December 13, 2012 filed Facilitated Processing for Controlling Bonding Between Sheet and of U.S. Provisional No. 61 / 736,880 Patent Application Serial No. Carrier (hereinafter US'880), the controlled The joint area is formed by controlling the van der Waals bonding and/or hydrogen bonding between the carrier and the thin glass sheet, but still uses a covalent bonding region. Thus, while the articles and methods for processing sheets and carriers in US '727 and US '880 are capable of withstanding the harsh environment of FPD processing, it is undesirable for some applications due to thin glass and glass carriers. Strong covalent bonds in the joint region prevent re-use of the carrier by covalent bonding of, for example, Si-O-Si, with an adhesion of about 1000-2000 mJ/m ² (about glass) Breaking strength) to join. The swaying or peeling cannot be used to separate the covalently bonded portion of the thin glass from the carrier, and therefore, the entire sheet cannot be removed from the carrier. Alternatively, the non-joined area on which the device is mounted is scribed and extracted to leave a bonded perimeter of the thin glass sheet on the carrier.

In view of the above, there is a need for a sheet-and-carriage article that can withstand the harsh conditions of FPD processing including high temperature processing (there is no outgassing that is incompatible with the semiconductor or display fabrication process in which the sheet-carrier article is used), But allowed The entire area of the sheet is removed from the carrier (disposed one time, or partially removed) to allow the carrier to be reused for processing another sheet. This specification describes the manner in which the adhesion between the carrier and the sheet is controlled to create a temporary bond that is strong enough to be preserved in FPD processing (including LTPS processing) but weak enough to allow the sheet even after high temperature processing. Disengagement from the carrier. Such controlled engagement can be utilized to create an article having a reusable carrier, or alternatively to produce an article having a controlled bond and covalently bonded patterned region between the carrier and the sheet. More specifically, the present disclosure provides surface modifying layers (including various materials and associated surface heat treatments) that can be provided on, on, or both of the sheets to control the room temperature between the sheets and the carrier. Both wattage bonding and/or hydrogen bonding and high temperature covalent bonding. Even more precisely, the room temperature bonding can be controlled to hold the sheet and carrier together during vacuum processing, wet processing, and/or ultrasonic cleaning processes. At the same time, high temperature covalent bonding can be controlled to prevent permanent bonding between the sheet and the carrier during high temperature processing, as well as maintaining sufficient bonding to prevent delamination during high temperature processing. In an alternate embodiment, the surface modifying layer can be used to create a variety of controlled joint regions (where the carrier and sheet remain fully joined through various processes including vacuum processing, wet processing, and/or ultrasonic cleaning). Processing) along with covalent bonding regions to provide other processing options, for example, maintaining the airtightness between the carrier and the sheet even after dicing the article into small pieces for additional device processing. In addition, some surface modifying layers provide control of the bond between the carrier and the sheet while reducing degassing emissions during harsh conditions in an FPD (eg, LTPS) processing environment, such as high temperatures. And / or vacuum processing. Additionally, in alternative embodiments, some surface modifying layers can be used to have a glass bonded surface The carrier is adapted to controllably engage a sheet having a polymeric bonding surface. The polymeric bonding surface can be part of a polymer sheet on which electrons or other structures are formed, or alternatively, the polymeric bonding surface can be part of a composite sheet comprising a glass layer on which electrons are formed or Other structures.

Other features and advantages will be set forth in the description which follows, and in the <RTIgt; Various aspects of the illustrations are made to recognize such features and advantages. It is to be understood that the foregoing general descriptions

A further understanding of the principles of the invention will be set forth in the <RTIgt; The drawings illustrate one or more embodiments and, together with the It is to be understood that the various features disclosed in the specification and in the drawings can be used in any and all combinations. By way of non-limiting example, various features may be combined with one another as set forth in the appended claims.

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Figure 1 is a schematic side elevational view of an article having a carrier bonded to a sheet having a surface modifying layer between the carrier and the sheet.

Fig. 2 is a development and partial cross-sectional view of the object in Fig. 1.

Figure 3 is a graph of the concentration of surface hydroxyl groups on cerium oxide as a function of temperature.

Figure 4 shows the surface energy of SC1-clean glass as the annealing temperature changes. Chart of the transformation.

Figure 5 is a graph of the surface energy of a thin fluoropolymer film deposited on a glass sheet as a function of the percentage of one of the constituent materials from which the film is made.

Figure 6 is a schematic plan view of a sheet joined to a carrier by a joint region.

Figure 7 is a schematic side view of a stack of glass sheets.

Figure 8 is an expanded view of one embodiment of the stack in Figure 7.

Figure 9 is a schematic diagram of the test device.

Figure 10 is a series of graphs showing the relative energy of surface energy (surface energy of different parts of the test apparatus of Figure 9) for various materials under different conditions.

Figure 11 is a graph of % bubble area change versus temperature for various materials.

Figure 12 is another graph of % bubble area change versus temperature for various materials.

Figure 13 is a graph of the surface energy of a fluoropolymer film deposited on a glass sheet as a function of the percentage of one of the gases used during deposition.

Figure 13A is a graph of the surface energy of a fluoropolymer film deposited on a glass sheet as a function of the percentage of one of the gases used during deposition.

Figure 14 is a graph of surface energy versus deposition time for a surface modifying layer.

Figure 15 is a graph of thickness vs. deposition time on a double logarithmic scale for a surface modifying layer.

Figure 16 shows the relative energy of the surface energy for different surface modification layers. A chart of temperature.

Figure 17 is a graph of the surface coverage of the surface modification layer.

Figure 18 is a summary of the efficacy of an organic transistor fabricated on a 200 micron PEN film bonded to a glass carrier.

In the following detailed description, exemplary embodiments of the invention are in the However, it is apparent to those skilled in the art that the present invention may be practiced in other embodiments without departing from the specific details disclosed herein. In addition, descriptions of well-known devices, methods, and materials may be omitted so as not to obscure the description of the various principles of the invention. Finally, the same element symbols refer to the same elements, wherever applicable.

Ranges may be expressed herein as "about" a particular value, and/or to "about" another particular value. When describing this range, another embodiment includes from a particular value and/or to another particular value. Similarly, when values are expressed as approximations, the use of the It should be further understood that the endpoints of each of the ranges are meaningful relative to the other endpoint and independent of the other endpoint.

The directional terms as used herein - for example, up, down, left, right, front, back, top, bottom - are only referenced to the drawing, and are not intended to imply absolute orientation.

As used herein, the singular forms "" Therefore, for example, reference to "a component" includes two or two unless the context clearly indicates otherwise. The above aspects of these "components".

In both US '727 and US '880, a solution is provided that allows for the processing of thin glass sheets on a carrier, whereby at least a portion of the thin glass sheets remain "unjoined" so that the device can be processed on a thin glass sheet. Removed from the carrier. However, the periphery of the thin glass is permanently (or covalently, or airtightly) bonded to the carrier glass via the formation of covalent Si-O-Si bonds. This covalently bonded perimeter prevents reuse of the carrier because the thin glass in this permanent joint cannot be removed without damaging the thin glass and the carrier.

To maintain favorable surface shape characteristics, the carrier is typically a display grade glass substrate. Therefore, in some cases, disposing of the carrier only after one use is wasteful and costly. Therefore, in order to reduce the cost of display manufacturing, it is desirable to be able to reuse the carrier to process more than one sheet substrate. The present disclosure sets forth articles and methods for allowing sheets to be processed through harsh environments including high temperature processing in FPD processing lines - where high temperature processing is Treated at a temperature of 400 ° C, and may vary depending on the type of device being fabricated, for example, up to about at least in the gallium or amorphous indium gallium zinc oxide (IGZO) backsheet treatment The temperature of 450 ° C is up to about 500-550 ° C in the crystalline IGZO treatment, or as typical as in the LTPS process, up to about 600-650 ° C - and still allows the sheet to be easily removed from the carrier without Destruction of the sheet or carrier (eg, where one of the carrier and sheet is broken or cracked into two or more pieces) whereby the carrier can be reused.

As shown in Figures 1 and 2, the article 2 has a thickness 8 and includes a carrier 10 having a thickness 18 and a sheet 20 having a thickness 28 (i.e., having A sheet having a thickness of 300 microns, including but not limited to, for example, the following thicknesses: 10-50 microns, 50-100 microns, 100-150 microns, 150-300 microns, 300, 250, 200, 190, 180, 170, 160 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20 or 10 microns), and a surface modifying layer 30 having a thickness 38. Object 2 is designed to allow for designing for thicker sheets (ie, about .4 mm, for example, .4 mm, .5 mm, .6 mm, .7 mm, .8 mm, .9 mm, or 1.0 mm of the sheets are processed in the sheet 20, although the sheet 20 itself 300 microns. That is, the thickness 8 of the sum of the thicknesses 18, 28, and 38 is designed to be equal to the thickness of the thicker sheet, and one piece of equipment - for example, equipment designed to place the electronic device components on the substrate sheet - Designed to handle this thicker sheet. For example, if the processing equipment is designed for a 700 micron sheet and the sheet has a thickness 28 of 300 microns, the thickness 18 would be chosen to be 400 microns assuming a negligible thickness 38. That is, the surface modifying layer 30 is not shown to scale; instead, the surface modifying layer is greatly exaggerated for illustrative purposes only. In addition, the surface modifying layer is shown in cross section. In fact, when a reusable carrier is provided, the surface modifying layer will be evenly disposed on the bonding surface 14. Typically, thickness 38 will be on the order of a few nanometers, such as 0.1 to 2.0 nm or up to 10 nm, and in some cases, up to 100 nm. The thickness 38 can be measured by ellipsometry. In addition, the presence of the surface modifying layer can be detected by surface chemical analysis, for example by ToF Sims mass spectrometry. Thus, the contribution of thickness 38 to the thickness 8 of the article is negligible and may be omitted in the calculation for determining the suitable thickness 18 of the carrier 10 for processing a given sheet 20 having a thickness of 28. However, to the extent that the surface modifying layer 30 has any significant thickness 38, this thickness can be considered for determining the thickness 18 of the carrier 10 for a given thickness 28 of the sheet 20 and a given thickness for which the processing equipment is designed.

The carrier 10 has a first surface 12, an engagement surface 14, a perimeter 16 and a thickness 18. Additionally, carrier 10 can have any suitable material including, for example, glass. The carrier need not be glass, but may alternatively be ceramic, glass-ceramic or metal (because the surface energy and/or bonding may be controlled in a manner similar to that described below in connection with the glass carrier). If the carrier 10 is made of glass, the carrier may have any suitable composition, including aluminosilicate, borosilicate, aluminoboronate, sodium calcium citrate, and may be an alkali metal or Alkali-free, depending on its end use. The thickness 18 can be about 0.2 to 3 mm or greater, such as 0.2, 0.3, 0.4, 0.5, 0.6, 0.65, 0.7, 1.0, 2.0, or 3 mm or greater, and will depend on the thickness 28 and thickness 38 (as noted above, When this thickness is not negligible, this is the case). Additionally, the carrier 10 can be formed from one layer as shown, or from a plurality of layers joined together (including a plurality of sheets of the same or different materials). In addition, the carrier may have a Gen 1 size or larger, for example, Gen 2, Gen 3, Gen 4, Gen 5, Gen 8 or larger (for example, 100 mm x 100 mm to 3 m x 3 m or more) Sheet size).

Sheet 20 has a first surface 22, an engagement surface 24, a perimeter 26, and a thickness 28. The perimeters 16 and 26 can have any suitable shape, can be identical to one another, or can be different from one another. Additionally, the sheet 20 can have any suitable material including, for example, glass, ceramic or glass-ceramic. In some cases, the sheet 20 can be a polymer or a composite sheet having a polymeric and/or glass bonded surface. When the sheet 20 is made of glass, the sheet may have any suitable composition, including aluminosilicates, borosilicates, aluminoboronates, soda-calcium silicates, and may be alkali-containing or non-containing. Alkali metal, depending on its end use. Thermal expansion coefficient of the sheet It can be relatively closely matched to the coefficient of thermal expansion of the carrier to prevent warpage of the article during processing at elevated temperatures. When the article 2 is processed at a lower temperature, i.e., where the CTE match is not such a concern, the polymer sheet can be used with a glass carrier. Of course, there may be other situations where the polymeric sheet can be used with a glass carrier. As indicated above, the thickness 28 of the sheet 20 is 300 microns or less. In addition, the sheet may have a Gen 1 size or larger, for example, Gen 2, Gen 3, Gen 4, Gen 5, Gen 8 or larger (for example, a piece of 100 mm x 100 mm to 3 m x 3 m or more) Material size).

The article 2 not only needs to have the correct thickness to be disposed of in existing equipment, but sometimes it will also need to be preserved in the harsh environment in which it can be handled. For example, flat panel display (FPD) processing can include wet processing, ultrasonic processing, vacuum processing, and in some cases high temperatures (eg, 400 ° C) treatment. For some processes, as noted above, the temperature can be 500 ° C, or 600 ° C and up to 650 ° C.

In order to preserve in the harsh environment in which the article 2 will be treated, such as during fabrication of, for example, FPD, the bonding surface 14 should be joined to the bonding surface 24 with sufficient strength that the sheet 20 is not separated from the carrier 10. Moreover, this strength should be maintained during processing so that the sheet 20 is not separated from the carrier 10 during processing. Additionally, to allow the sheet 20 to be removed from the carrier 10 (so that the carrier 10 can be reused), the engagement surface 14 should not be created by initial design engagement forces and/or by modification of the initial design engagement force. Engagement force (eg, can be processed, for example, when the article is subjected to high temperatures, for example, experienced in Occurs when processed at a temperature of 400 ° C) is too strongly bonded to the bonding surface 24 . The surface modifying layer 30 can be used to control the joint strength between the joining surface 14 and the joining surface 24 in order to achieve both of these goals. The controlled bonding force is achieved by controlling the contribution of van der Waals force (and/or hydrogen bonding) and covalent attraction energy to the total adhesion energy by modulating the sheet 20 and the carrier 10 Polar and non-polar surface energy components are controlled. This controlled joint is strong enough for FPD processing (including wet process, ultrasonic process, vacuum process, and thermal process, including 400 ° C temperature, and in some cases, 500 ° C or The processing is maintained at 600 ° C and at a processing temperature of up to 650 ° C and remains uncoupled by the application of sufficient separation force and also by the force that does not cause catastrophic damage to the sheet 20 and/or the carrier 10. Such disengagement allows removal of the sheet 20 and the device made thereon, and also allows for repeated use of the carrier 10.

Although the surface modifying layer 30 is shown as a solid layer between the sheet 20 and the carrier 10, this need not be the case. For example, layer 30 can be about 0.1 to 2 nm thick and can not completely cover each bit of bonding surface 14. For example, the coverage rate can be 100%, 1% to 100%, 10% to 100%, 20% to 90% or 50% to 90%. In other embodiments, layer 30 can be up to 10 nm thick, or in other embodiments, even up to 100 nm thick. The surface modifying layer 30 can be considered to be disposed between the carrier 10 and the sheet 20, although it may not contact any of the carrier 10 and the sheet 20. In any event, an important aspect of the surface modifying layer 30 is its ability to bond the bonding surface 14 to the bonding surface 24, thereby controlling the strength of the bond between the carrier 10 and the sheet 20. The material and thickness of the surface modifying layer 30, as well as the treatment of the joining surfaces 14, 24 prior to joining, can be used to control the strength of the bond (energy of adhesion) between the carrier 10 and the sheet 20.

In general, the energy of adhesion between two surfaces is given by ("A theory for the estimation of surface and interfacial energies. I. derivation and application to interfacial tension", LAGirifalco and RJGood, J. Phys. Chem. , V 61, p904): W = Y ₁ + Y ₂ - Y ₁₂ (1) wherein Y ₁ , Y ₂ and Y ₁₂ are the surface energy of the surface 1, the surface 2 and the interface energy of the surface 1 and the surface 2, respectively. The individual surface energy is usually a combination of two terms; that is, the dispersion component γ ^d and the polar component γ ^p Y = Y ^d + Y ^p (2)

When the adhesion major is attributed to the London dispersive force (γ ^d ) and the polar force (γ ^p ) such as hydrogen bonding, the interfacial energy can be given by (Girifalco and RJGood, as mentioned above):

After substituting (3) into (1), the energy of adhesion can be roughly calculated as:

In the above equation (4), only the van der Waals force (and/or hydrogen bonding) component of the adhesion energy is considered. These components include polar-polar interactions (Keesom), polar-nonpolar interactions (Debye), and non-polar-nonpolar interactions (London). However, other attractive energies may also be present, such as covalent bonding and electrostatic bonding. Therefore, in a more general form, the above equation is written as: Where w _c and w _e are covalent and electrostatic adhesion energy. Covalent adhesion energy is quite common, as is common in tantalum wafer bonding, where a pair of initial hydrogen bonded wafers are heated to a higher temperature to convert most or all of the sterol-sterol hydrogen bonds to Si- O-Si covalent bond. Although the initial, room temperature hydrogen bonding produces an adhesion energy of about 100-200 mJ/m ² that allows separation of the bonding surfaces, a complete covalent bond crystal circle pair as achieved during high temperature processing (about 400 to 800 ° C). There is an adhesion energy of about 1000-3000 mJ/m ² which does not allow separation of the bonding surfaces; instead, the two wafers act as monoliths. On the other hand, if the two surfaces are completely coated with a low surface energy material such as a fluoropolymer (the thickness of which is large enough to shield the underlying substrate), the adhesion energy will be the adhesion energy of the coating material and will be Extremely low, resulting in low or no adhesion between the bonding surfaces 14, 24, whereby the sheet 20 cannot be processed in the carrier 10. Consider two extreme conditions: (a) Two standard cleanings 1 (SC1, known in the art) clean the glass surface, which is saturated with sterol groups and joined together via hydrogen bonding at room temperature (by means of adhesion energy) 100-200 mJ/m ² ), followed by heating to a high temperature at which the sterol group is converted to a covalent Si-O-Si bond (by which the adhesion energy becomes 1000-3000 mJ/m ² ). Thereafter, an adhesive energy is too high for a pair of glass surfaces to be detached; and (b) two glass surfaces coated entirely with a fluoropolymer having a low surface adhesion energy (about 12 mJ/m ² per surface), It is joined at room temperature and heated to a high temperature. In this latter condition (b), the surface is not only not joined (because the total adhesion energy of about 24 mJ/m ² is too low when the surfaces are placed together), and the surfaces are not joined at high temperatures because they do not exist. (or very few) polar reactive groups. Between these two extremes, there is a range of adhesive energies, for example between 50 and 1000 mJ/m ² , which produces a desired degree of controlled bonding. Accordingly, the inventors have discovered various ways of providing an adjustable surface modifying layer 30 that produces adhesive energy between these two extremes and that enables controlled engagement, which is controlled The bonding is sufficient to maintain a pair of glass substrates (e.g., glass carrier 10 and thin glass sheet 20) engaged with one another during the harsh conditions of FPD processing, and the extent of the controlled engagement (even at example, for example After the high temperature treatment at 400 ° C) the detachment of the sheet 20 from the carrier 10 is allowed after the treatment is completed. Moreover, the detachment of the sheet 20 from the carrier 10 can be performed by mechanical force and is performed in a manner that does not have devastating damage to at least the sheet 20, and preferably also does not cause devastating damage to the carrier 10. .

Equation (5) describes: Adhesive energy is a function of four surface energy parameters plus covalent and electrostatic energy, if any.

Appropriate adhesion energy can be achieved by a sensible selection of surface modifiers, i.e., surface modification layer 30, and/or heat treatment of the surface prior to bonding. Appropriate adhesion energy can be obtained by the selection of a chemical modifier for one or both of the bonding surface 14 and the bonding surface 24, which in turn controls the van der Waals force (and/or hydrogen bonding, Because such terms are used interchangeably throughout the specification, as well as adhesion energy and processing by high temperatures (eg, approximately Possible covalent bond bonding energy caused by 400 ° C). For example, SC1 cleans the bonding surface of the glass (which is initially saturated with sterol groups, has a high polarity component of surface energy) and is coated with a low energy fluoropolymer, which provides for the surface by polar and non-polar groups. Control of fractional coverage. This not only provides control of the initial van der Waals bonding (and/or hydrogen bonding) at room temperature, but also provides control over the extent/degree of covalent bonding at higher temperatures. Performing control of the initial van der Waals joint (and/or hydrogen bonding) at room temperature to provide a surface to the other surface to allow vacuum processing and or spin-rinse (spin-rinse) -dry;SRD) type treatment, and in some cases also provides an easy-to-form bond between the surface and the other surface - wherein the easy-to-form bond can be applied externally at room temperature without the entire area of the sheet 20 In the case of a force (such as the case where the sheet 20 is pressed into the carrier 10), it is performed using a squeegee or using a reduced pressure environment. That is, the initial Van der Waals joint provides at least a minimum degree of engagement that holds the sheet and carrier together so that they do not separate if one is held by one and the other is subjected to gravity. In most cases, the initial van der Waals bonding (and/or hydrogen bonding) will have a range that allows the article to undergo vacuum processing, SRD processing, and ultrasonic processing without delaminating the wafer from the carrier. Passing through the surface modifying layer 30 (including the material from which the surface modifying layer is made and/or the surface treatment of the surface on which the surface modifying layer is applied) and/or by bonding the surface before joining the surfaces together The heat treatment achieves the desired adhesion energy for such precise control of van der Waals (and/or hydrogen bonding) and covalent interaction at an appropriate level, which allows the sheet 20 to engage the carrier 10 throughout the FPD type process, At the same time, the sheet 20 is allowed to separate from the carrier 10 after the FPD type treatment (by avoiding the appropriate force to damage the sheet 20 and/or the carrier). Additionally, where appropriate, an electrostatic charge can be applied to one or both of the glass surfaces to provide another level of control of the adhesion energy.

FPD processing, such as p-Si and oxide TFT fabrication, typically involves a thermal process at temperatures above 400 ° C, above 500 ° C and in some cases at 600 ° C or above 600 ° C, up to 650 ° C. The isothermal temperature causes the thin glass sheet 20 to be bonded to the glass to glass of the glass carrier 10 in the absence of the surface modifying layer 30. Thus, controlling the formation of Si-O-Si bonds results in a reusable carrier. One method of controlling the formation of Si-O-Si bonds at elevated temperatures is to reduce the concentration of surface hydroxyl groups on the surface to be joined.

As shown in Fig. 3, the graph is an Iler's plot of the surface hydroxyl concentration on cerium oxide as a function of temperature (RKIller: The Chemistry of Silica (Wiley-Interscience, New York, 1979), hydroxyl groups per square nm ( OH The number of bases decreases as the temperature of the surface increases. Thus, heating the cerium oxide surface (and heating the glass surface by similar means, such as bonding surface 14 and/or bonding surface 24) reduces the concentration of surface hydroxyl groups, thereby reducing the probability of hydroxyl interactions on the two glass surfaces. This reduction in surface hydroxyl concentration, in turn, reduces the Si-O-Si bond formed per unit area, thereby reducing adhesion. However, the elimination of surface hydroxyl groups requires long annealing times at elevated temperatures (above 750 ° C to completely eliminate surface hydroxyl groups). This long annealing time and high annealing temperature result in an expensive process and an impractical process because it may be higher than the strain point of a typical display glass.

From the above analysis, the inventors have found that objects including sheets and carriers suitable for FPD processing (including LTPS processing) can be made by balancing the following three concepts: (1) by controlling the initial room temperature bonding Modifications with and/or sheet bonding surfaces that can be performed by controlling van der Waals bonding (and/or hydrogen bonding) to produce moderate adhesion energy (eg, having each surface prior to surface bonding) 40 mJ/m ² of surface energy) to promote initial room temperature bonding, and sufficient to preserve in a non-high temperature FPD process, such as vacuum processing, SRD processing, and/or ultrasonic processing; (2) in one way Surface modification of the sheet and/or sheet, which is thermally stable for preservation in the FPD process without degassing, which can cause delamination and/or unacceptable contamination in the fabrication of the device, for example, Unacceptable contamination of the semiconductor and/or display fabrication process using the article; and (3) controlling bonding at elevated temperatures by controlling the concentration of hydroxyl groups on the surface of the carrier and being capable of high temperatures (eg, The concentration of other substances forming a strong covalent bond at a temperature of 400 ° C, whereby the bonding energy between the bonding surface of the carrier and the bonding surface of the sheet can be controlled so that even at high temperatures (especially at 500-650) After the thermal process in the °C range, as in the FPD process, the adhesion between the carrier and the sheet is maintained within a range that allows for the use without damaging at least the sheet (and preferably without destroying the sheet or carrier). The separation force of either) disengages the sheet from the carrier and is still sufficient to maintain the bond between the carrier and the sheet so that the carrier and the sheet do not delaminate during processing.

In addition, the inventors have discovered that the use of the surface modifying layer 30 (together with the bonding surface as appropriate) can balance the above concepts in order to easily achieve a controlled joint area, i.e., provide sufficient between the sheet 20 and the carrier 10. The joint area is joined at room temperature to allow the article 2 to be processed in an FPD type process (including vacuum process and wet process) and between the control sheet 20 and the carrier 10 (even in Covalently bonded bonding regions at a high temperature of 400 ° C to allow removal of the sheet 20 from the carrier 10 after the article 2 has completed high temperature processing (eg, FPD type processing or LTPS processing) (without Destruction, and preferably no damage to the vehicle). A series of tests were used to evaluate potential joint surface preparation and surface modification layers that would provide reusable carriers for FPD processing. Different FPD applications have different requirements, but at this point the LTPS and oxide TFT processes appear to be the most stringent, and therefore the tests that represent the steps in such processes are chosen because these tests are the applications of the object 2. Vacuum processes, wet cleaning (including SRD processes and ultrasonic type processes) and wet etching are common to many FPD applications. Typical Si TFT fabrication requires processing up to 320 °C. Annealing at 400 ° C is used for the oxide TFT process, while the crystallization and dopant activation steps above 600 ° C are used for the LTPS process. Therefore, the following five tests were used to evaluate the possibility that the particular joint surface preparation and surface modification layer 30 allowed the sheet 20 to remain bonded to the carrier 10 throughout the FPD process, while at the same time (including in The sheet 20 is allowed to be removed from the carrier 10 after treatment at a temperature of 400 ° C (without breaking the sheet 20 and/or the carrier 10). The test is performed in sequence, and the sample is sent from one test to the next unless there is a failure of the type that does not allow subsequent tests.

(1) Vacuum test. Vacuum compatibility testing was performed in an STS multiplexed PECVD load lock chamber (available from SPTS, Newport, UK) - the Ebara A10S dry pump with soft pump valve (available from Ebara) Technologies Inc., Sacramento, CA) pumped. The sample was placed in a load lock chamber and the load lock chamber was then pumped from atmospheric pressure to 70 mTorr in 45 sec. The failure indicated by the notation "F" in the "vacuum" column of the following table is deemed to have occurred in the following cases: (a) the loss of adhesion between the carrier and the sheet (according to visual inspection using the naked eye, In the case where the sheet has been dropped from the carrier or partially disengaged from the carrier, it is considered to have failed; (b) foaming between the carrier and the sheet (eg, by visual inspection using the naked eye) - taking photographs of the sample before and after processing, and then comparing, determining that a failure has occurred if the size of the defect increases in size visible to the naked eye; or (c) moving the sheet relative to the carrier (eg, borrowing Determined by visual inspection with the naked eye - photographs were taken of the samples before and after the test, where failure was considered to have occurred in the following cases: there was movement of joint defects such as bubbles, or edge disengagement, or presence on the carrier The movement of the sheet). In the table below, the notation "P" in the "Vacuum" column indicates that the sample has not expired according to previous guidelines.

(2) Wet process test. Use Semitool SRD-470S (available Wet process compatibility testing was performed from Applied Materials, Santa Clara, CA). The test consisted of 60 seconds of 500 rpm cleaning, Q-cleaning to 15 MOhm-cm at 500 rpm, 10 seconds of rinsing at 500 rpm, drying at 1800 rpm for 90 seconds under warm nitrogen and 180 seconds at 2400 rpm. The failure indicated by the notation "F" in the "SRD" column of the following table is deemed to have occurred in the following cases: (a) the loss of adhesion between the carrier and the sheet (according to visual inspection using the naked eye, In the case where the sheet has been dropped from the carrier or partially disengaged from the carrier, it is considered to have failed; (b) foaming between the carrier and the sheet (eg, by visual inspection using the naked eye) - taking photographs of the sample before and after processing, and then comparing, determining that a failure has occurred if the size of the defect increases in size visible to the naked eye; or (c) moving the sheet relative to the carrier (eg, borrowing Determined by visual inspection with the naked eye - photographs were taken of the samples before and after the test, where failure was considered to have occurred in the following cases: there was movement of joint defects such as bubbles, or edge disengagement, or presence on the carrier Or (d) the penetration of water under the sheet (as judged by visual inspection at 50x using an optical microscope, where the failure has been determined if the liquid or residue is observable) . In the table below, the notation "P" in the "SRD" column indicates that the sample has not expired according to previous criteria.

(3) Temperature test up to 400 °C. The 400 °C process compatibility test was performed using an Alwin 21 Accuthermo 610 RTP (available from Alwin 21, Santa Clara CA). The carrier having the sheet joined thereto was cycled from room temperature at 6.2 ° C/min to 400 ° C in the chamber, held at 400 ° C for 600 seconds, and cooled to 300 ° C at 1 ° C/min. The carrier and sheet were then allowed to cool to room temperature. The failure indicated by the notation "F" in the "400 ° C" column of the following table is deemed to have occurred in the following cases: (a) the loss of adhesion between the carrier and the sheet (according to visual inspection by the naked eye, Where in the case where the sheet has been dropped from the carrier or partially disengaged from the carrier, it is considered to have failed; (b) foaming between the carrier and the sheet (eg by visual inspection by the naked eye) Judgment--taking a photograph of the sample before and after processing, and then comparing, determining that a failure has occurred in the case where the size of the defect increases in size visible to the naked eye; or (c) an increase between the carrier and the sheet Adhesive, whereby the increased adhesion prevents disengagement of the sheet from the carrier (by insertion of the blade between the sheet and the carrier, and/or by lengthing a piece 1"6"(2-3" 100mm square attached to the thin glass when the Kapton ^TM tape (from Saint Gobain Performance Plastic, Hoosik NY series of K102) bonding to the sheet, and pulling on the tape) without breaking the sheet or carrier, wherein the carrier sheet and attempt to separate In the case where the sheet or the carrier is damaged, In the event that the sheet and carrier are not disengageable by any of the disengagement methods, failure is considered to have occurred. Additionally, after the sheet is engaged with the carrier, and prior to thermal cycling, the representative sample is taken off. Bonding tests to determine that a particular material including any associated surface treatment allows the sheet to be disengaged from the carrier prior to temperature cycling. In the table below, the notation "P" in the "400 ° C" column indicates: according to previous criteria, the sample Not expired.

(4) Temperature test up to 600 °C. Perform 600 °C process compatibility testing with Alwin21 Accuthermo610 RTP. The carrier with the sheet was heated in a chamber from room temperature at 9.5 ° C/min to 600 ° C, held at 600 ° C for 600 seconds, and then cooled to 300 ° C at 1 ° C/min. The carrier and sheet were then allowed to cool to room temperature. The failure indicated by the notation "F" in the "600 ° C" column of the following table is deemed to have occurred in the following cases: (a) the loss of adhesion between the carrier and the sheet (according to visual inspection by the naked eye, Where in the case where the sheet has been dropped from the carrier or partially disengaged from the carrier, it is considered to have failed; (b) foaming between the carrier and the sheet (eg by visual inspection by the naked eye) Judgment--taking a photograph of the sample before and after processing, and then comparing, determining that a failure has occurred in the case where the size of the defect increases in size visible to the naked eye; or (c) an increase between the carrier and the sheet adhesive, thereby increasing the adhesion of this carrier sheet and prevents the disengage (by sheet inserted between the blade and the carrier and / or Kapton ^TM tape by the adhesive to a sheet as described above, and pulls Tape) without damaging the sheet or carrier, where there is damage to the sheet or the carrier when attempting to separate the sheet from the carrier, or the sheet and carrier are not executable by any disengagement method In the case of disengagement, it is considered to have failed . Additionally, after the sheet is bonded to the carrier, and prior to thermal cycling, a de-bonding test is performed on the representative sample to determine that the particular material and any associated surface treatments allow the sheet to disengage from the carrier prior to temperature cycling. In the table below, the notation "P" in the "600 °C" column indicates that the sample has not expired according to the previous guidelines.

(5) Ultrasonic testing. The ultrasonic compatibility test is performed by cleaning the articles in a four-slot pipeline in which the articles are processed sequentially in each of the slots from slot #1 to slot #4. For each of the four slots, the slot size is 18.4"L x 10"W x 15"D. The two cleaning slots (#1 and #2) contain 1% Semiclean in DI water at 50 °C KG, which is commercially available from Yokohama Oils and Fats Industry Co Ltd., Yokohama Japan. The cleaning tank #1 is agitated using a NEY prosonik 2 104 kHz ultrasonic generator (available from Blackstone-NEY Ultrasonics, Jamestown, NY), and utilizes NEY prosonik 2 104kHz ultrasonic generator Stir the cleaning tank #2. The two cleaning tanks (tank #3 and tank #4) contain DI water at 50 °C. The cleaning tank #3 was agitated by a NEY sweepsonik 2D 72 kHz ultrasonic generator, and the cleaning tank #4 was agitated by a NEY sweepsonik 2D 104 kHz ultrasonic generator. The process was carried out for 10 min in each of the tanks #1-4, followed by spin-drying (SRD) after removing the sample from the tank #4. The failure indicated by the notation "F" in the "Ultrasonic" column of the following table is deemed to have occurred in the following cases: (a) the loss of adhesion between the carrier and the sheet (according to visual inspection by the naked eye, Where in the case where the sheet has been dropped from the carrier or partially disengaged from the carrier, it is considered to have failed; (b) foaming between the carrier and the sheet (eg by visual inspection by the naked eye) Judgment--photographing the sample before and after processing, and then comparing, determining that a failure has occurred in the case where the size of the defect increases in size visible to the naked eye; or (c) formation of other gross defects ( As judged by visual inspection with a light microscope at 50x, in the case where particles captured between the thin glass and the carrier are not observed before the presence, it is judged that failure has occurred; or (d) water is under the sheet Penetration (as determined by visual inspection at 50x using an optical microscope, where the liquid or residue is observable, the failure has been determined. In the table below, the notation in the "Ultra-Optical" column" P" indication: according to Former criterion, the sample did not fail. In the following tables, blank samples indicative of "ultrasound" column of this test is not the way.

Joint energy test

The joining energy is the energy used to separate the sheet from the carrier. The bonding energy can be measured in a variety of different ways. However, as used herein, the bonding energy is measured as follows.

The joint energy is measured using a double cantilever beam method (also known as a wedge method). In this method, a wedge having a known thickness is placed at the edge between the bonding sheet and the carrier glass. The wedge produces a characteristic delamination distance L. This delamination distance is measured and used to calculate the joint energy γ _BE in Equation 6.

The Young's modulus E of the EXG composition to both the carrier (1) and the sheet (2) was 73.6 GPa. The typical thickness t _s1 of the carrier is 0.7 mm, and the thickness t _s2 of the sheet is 0.13 mm. The Martor 37010.20 insert is used for a wedge consisting of a thickness t _w of 95 μm. A sample with very high bonding energy where pre-cracking with independent wedges. This allows for easier insertion of the wedge and generation of characteristic delamination lengths. For the reported joint energy data, a value of 2500 indicates the test-limit condition, and for a particular sample, the sheet cannot be disengaged from the carrier.

Preparation of a bonding surface by heating, reduced via hydroxyl groups

One or more of the bonded surfaces 14, 24 are modified with the surface modifying layer 30 so that the article 2 can successfully undergo FPD processing (i.e., wherein the sheet 20 remains bonded to the carrier 10 during processing, but includes high temperature processing The benefit of being able to be separated from the carrier 10 after processing is demonstrated by treating the article 2 having the glass carrier 10 and the thin glass sheet 20 without the surface modifying layer 30 therebetween. Specifically, the preparation of the bonding surfaces 14, 24 is first attempted by heating to reduce the hydroxyl groups but without the surface modifying layer 30. The carrier 10 and the sheet 20 are cleaned so that the joint surfaces 14 and 24 are joined to each other, and then the article 2 is tested. A typical cleaning process for preparing a glass for bonding is an SC1 cleaning process in which dilute hydrogen peroxide and a base (usually ammonium hydroxide, but can also be used) The glass is cleaned in a tetramethylammonium hydroxide solution such as JT Baker JTB-100 or JTB-111. Cleaning removes the particles from the bonded surface and obtains a known surface energy, i.e., it provides a baseline of surface energy. The cleaning method does not need to be SC1, and other types of cleaning can be used. For example, the type of cleaning may have only a minimal effect on the surface of the sterol group. The results of the various tests are listed in Table 1 below.

Strong but detachable initial room temperature bonding or van der Waals bonding and/or hydrogen bonding is produced by simply cleaning a thin glass piece of 100 mm square x 100 μm thick, and a glass carrier, ie 150 mm diameter a single mean flat (SMF) wafer of 0.50 or 0.63 mm thickness, the thin glass piece and the glass carrier each comprising Eagle XG® display glass (without alkali metal, aluminum borosilicate glass, An average surface roughness Ra of about 0.2 nm, which is commercially available from Corning Incorporated, Corning, NY). In this example, the glass was cleaned for 10 min in a bath of 40:1:2 DI water: JTB-111: hydrogen peroxide at 65 °C. A thin glass or glass carrier may or may not have been annealed in nitrogen for 10 min at 400 ° C to remove residual water - in the "Carriage" column or "Thin Glass" column in Table 1 below, "400"°C" indicates that the sample was annealed in nitrogen for 10 minutes at 400 °C. The FPD process compatibility test proves that the initial and room temperature bonding of this SC1-SC1 is mechanically strong enough to successfully complete the vacuum test, SRD test and ultrasonic test. However, heating at 400 ° C and above produces a permanent bond between the thin glass and the carrier, ie, the thin glass sheet cannot be self-destructed without destroying either or both of the thin glass sheet and the carrier. The vehicle is removed. Moreover, even for Example 1c, this is the case where each of the carrier and the thin glass is subjected to an annealing step to reduce the concentration of surface hydroxyl groups. Therefore, the bonding surfaces 14 and 24 are prepared by the above-described heating separately and then the bonding of the device 10 and the sheet 12 without the surface modifying layer 30 is not used for the FPD process (wherein the temperature will be Suitable for controlled joints at 400 ° C).

Preparation of a bonding surface by a hydroxyl group reduction and surface modification layer

The hydroxyl reduction as achieved by, for example, heat treatment and the surface modifying layer 30 can be used together to control the interaction of the bonding surfaces 14, 24. For example, the bonding energy of the bonding surfaces 14, 24 (for van derma bonding and/or hydrogen bonding at room temperature due to polarity/dispersion energy components, and covalent bonding due to covalent energy components at high temperatures) Controlled to provide varying bond strength between: where room temperature bonding is difficult, to allow easy room temperature bonding of the joint surface and where the joint surface separates after high temperature processing, to - at high temperatures After that - to prevent surface separation without damage. In some applications, it may be desirable to have no joints or have very weak joints (as when the surface is in a "non-joined" region), and the "non-joined" regions are described in the sheet/carrier concept of US '727. And as described below). In other applications, for example, for FPD processes and similar processes (where achievable) 500 ° C, or Reusable carrier at a process temperature of 600 ° C and up to 650 ° C. It is desirable to have sufficient van derma bonding and/or hydrogen bonding at room temperature to initially place the sheet and carrier Together, and still prevent or limit high temperature covalent bonding. For other applications, it may be desirable to have sufficient room temperature bonding to initially place the sheets and carriers together, and to create strong covalent bonds at elevated temperatures (eg, when the surface is in the "joining region") Thus, the "joining area" is described in the sheet/carrier concept of US '727 and is discussed below. Although not wishing to be bound by theory, in some cases, the surface modifying layer can be used to control the sheet and the initial placement of the carrier by which it is placed, while reducing the hydroxyl groups on the surface (eg, by heating the surface) Or, for example, by reacting a hydroxyl group with a surface modifying layer, can be used to control covalent bonding, especially covalent bonding at elevated temperatures.

The material for the surface modifying layer 30 can provide bonding surfaces 14, 24 having energy (eg, as measured for one surface, <40 mJ/m ² , and including polar and dispersed components), whereby the surface is only produced Weakly engaged. In one example, hexamethyldisilazane (HMDS) can be used to produce this low energy surface by reacting with surface hydroxyl groups to leave a trimethylsilyl (TMS) capped surface. The HMDS as a surface modifying layer can be used in conjunction with surface heating to reduce the hydroxyl concentration to control room temperature bonding and high temperature bonding. By selecting a suitable joint surface for each of the joint surfaces 14, 24, an article having a range of capabilities can be achieved. More specifically, in the case of providing a reusable carrier for LTPS processing, a suitable bond can be achieved between the thin glass sheet 20 and the glass carrier 10 for vacuum processing testing, SRD processing testing, 400 The °C (parts a and c) treatment test and each of the 600 °C (parts a and c) treatment tests were preserved (or successfully completed each).

In one example, the HMDS treatment of both the thin glass and the carrier after SC1 cleaning creates a weak joint surface, challenging the bonding with van der Waals (and/or hydrogen bonding) forces at room temperature. A mechanical force is applied to join the thin glass to the carrier. As shown in Example 2a of Table 2, this joint is very weak, so that The deflection of the carrier was observed in the vacuum test and the SRD treatment, and foaming was observed in the thermal processes at 400 ° C and 600 ° C (possibly due to degassing), and particle defects were observed after the ultrasonic treatment.

In another example, HMDS processing of only one surface (the carrier in the cited example) produced a stronger room temperature adhesion that was preserved in vacuum processing and SRD processing. However, a hot process at 400 ° C and above 400 ° C permanently bonds the thin glass to the carrier. This is not surprising since the hydroxyl concentration of 4.6-4.9/nm ² relative to fully hydroxylated cerium oxide has been calculated by Sindorf and Maciel in J. Phys. Chem. 1982, 86, 5208-5219. The maximum surface coverage of the trimethylsulfonyl group on cerium oxide was 2.8/nm ² and was measured by Suratwala et al. in Journal of Non-Crystalline Solids 316 (2003) 349-363 to be 2.7/nm ² . That is, although the trimethyldecyl group is bonded to some surface hydroxyl groups, some unbonded hydroxyl groups will remain. Thus, given sufficient time and temperature, condensation of the surface sterol groups will be expected to permanently bond the thin glass and carrier.

The altered surface energy can be generated by heating the glass surface to reduce the surface hydroxyl concentration prior to HMDS exposure, resulting in an increased polar component of surface energy. This reduces the driving force for forming covalent Si-O-Si bonds at high temperatures and produces stronger room temperature bonds, such as van der Waals bonding (and/or hydrogen bonding). Figure 4 shows the surface energy of the Eagle XG® display glass carrier after annealing and after HMDS treatment. The increased annealing temperature prior to HMDS exposure increases the total (polar and dispersed) surface energy after HMDS exposure by increasing the polarity distribution (line 404) (line 402). It can also be seen that the dispersion contribution to the total surface energy (line 406) remains largely unchanged by heat treatment. Although not wishing to accept On the constraint, but increasing the polar component of the energy in the surface after HMDS treatment and thus increasing the total energy appears to be due to the fact that some exposed glass surface regions exist due to sub-monolayer TMS coverage by HMDS even after HMDS treatment.

In Example 2b, the thin glass sheets were heated in a vacuum at a temperature of 150 ° C for one hour prior to bonding with the non-heat treated carrier having the coating of HMDS. This heat treatment of thin glass sheets is not enough to stop The glass sheet is permanently bonded to the carrier at a temperature of 400 °C.

As shown in Examples 2c-2e of Table 2, changing the annealing temperature of the glass surface prior to HMDS exposure can alter the bonding energy of the glass surface to control the bond between the glass carrier and the thin glass sheet.

In Example 2c, the carrier was annealed in a vacuum at 190 ° C for 1 hour, followed by HMDS exposure to provide a surface modifying layer 30. Further, the thin glass piece was annealed in a vacuum at 450 ° C for 1 hour, and then joined to the carrier. The obtained articles were preserved in a vacuum test, an SRD test, and at 400 ° C (parts a and c, but did not successfully complete part b because of increased foaming), but failed in the 600 ° C test. Thus, although there is increased resistance to high temperature bonding as compared to Example 2b, this is not sufficient to produce An article (e.g., LTPS treated) is processed at a temperature of 600 ° C, wherein the carrier is reusable.

In Example 2d, the carrier was annealed in vacuum for 1 hour at 340 °C, followed by HMDS exposure to provide a surface modifying layer 30. Again, the thin glass sheets were annealed in vacuum for 1 hour at 450 ° C before bonding to the carrier. The results were similar to those of Example 2c, in which the articles were in vacuum test, SRD test and 400 ° C (parts a and c, but did not successfully complete part b, because there was an increase The blistering is guaranteed, but it fails in the 600 °C test.

As shown in Example 2e, both the thin glass and the carrier were annealed in vacuum for 1 hr at 450 ° C, followed by HMDS exposure of the carrier and subsequent bonding of the carrier and the thin glass sheet, which improved the temperature resistance to permanent bonding. . Annealing both surfaces to 450 ° C prevented permanent bonding after RTP annealing at 600 ° C for 10 min, ie, the sample successfully completed the 600 ° C treatment test (parts a and c, but failed to pass part b because there was an increase Bubble; similar results were found for the 400 ° C test).

In Examples 2a through 2e above, each of the carrier and the sheet was Eagle XG® glass, wherein the carrier was a 630 micron thick 150 mm diameter SMF wafer and the sheet was 100 mm squared and 100 microns thick. HMDS was applied by pulsed vapor deposition in a YES-5 HMDS oven (available from Yield Engineering Systems, San Jose CA) and was an atomic layer thickness (i.e., about 0.2 to 1 nm) despite surface coverage. It may be smaller than a single layer, i.e., some of the surface hydroxyl groups are not covered by HMDS, as indicated by Maciel and as discussed above. Due to the small thickness of the surface modifying layer, there is almost no risk of degassing, which can cause contamination of the device. In addition, as indicated by the "SC1" notation in Table 2, each of the carrier and the sheet is cleaned using the SC1 process prior to heat treatment or any subsequent HMDS process.

A comparison between Example 2a and Example 2b shows: between the sheet and the carrier The bonding energy can be controlled by varying the number of surfaces including the surface modifying layer. Moreover, controlling the engagement energy can be used to control the engagement force between the two engagement surfaces. Furthermore, a comparison of Examples 2b-2e shows that the bonding energy of the surface can be controlled by varying the parameters of the heat treatment that is subjected to the heat treatment prior to application of the surface modifying material. Again, heat treatment can be used to reduce the amount of surface hydroxyl groups and thus control the extent of covalent bonding, especially the degree of covalent bonding at elevated temperatures.

Other materials that can act in different ways to control the surface energy on the bonding surface can be used in the surface modifying layer 30 to control the room temperature bonding force and the high temperature bonding force between the two surfaces. For example, if one or both of the bonding surfaces are modified with a surface modifying layer to produce a moderate bonding force, a reusable carrier can also be created that covers or spatially blocks substances such as hydroxyl groups to prevent A strong permanent covalent bond is formed between the carrier and the sheet at elevated temperatures. One way to produce a tunable surface energy and cover the surface hydroxyl groups to prevent the formation of covalent bonds is the deposition of a plasma polymer film such as a fluoropolymer film. Plasma polymerization from atmospheric or decompression and plasma excitation (DC or RF parallel plates, Inductively Coupled Plasma (ICP) Electron Cyclotron Resonance (ECR) downstream microwave or RF plasma) Gas deposition of thin polymer membranes such as fluorocarbon sources (including CF4, CHF3, C2F6, C3F6, C2F2, CH3F, C4F8, CFC or hydrochlorofluorocarbon), such as hydrocarbons of alkanes (including Methane, ethane, propane, butane), olefins (including ethylene, propylene), alkynes (including acetylene), and aromatic compounds (including benzene, toluene), hydrogen, and other sources of gas, such as SF6. Plasma polymerization produces a layer of highly crosslinked material. Control of the reaction conditions and source gases can be used to control film thickness, density, and chemistry to tailor the functional groups to be used.

Figure 5 shows the total surface energy (line 502) of a plasma polymerized fluoropolymer (PPFP) film deposited from a CF4-C4F8 mixture using an Oxford ICP380 etching tool (available from Oxford Instruments, Oxfordshire UK). Polar component (line 504) and dispersion component (line 506)). The film was deposited on Eagle XG® glass sheets and the spectral ellipsometry exhibited a film thickness of 1-10 nm. As seen in Figure 5, a glass carrier treated with a plasma polymerized fluoropolymer film containing less than 40% C4F8 exhibits a surface energy of >40 mJ/m ² and is joined by van der Waals at room temperature or hydrogen. Bonding between the thin glass and the carrier creates a controlled bond. When the carrier and the thin glass were initially joined at room temperature, a promoted joint was observed. That is, when the sheet is placed on the carrier and pressed together at one point, the wavefront travels across the carrier, but at an angle compared to the SC1 treated surface on which the surface modification layer is not present. At a lower speed. The controlled joint is sufficient to withstand all standard FPD processes, including vacuum process, wet process, ultrasonic process and thermal process up to 600 °C, ie the controlled joint successfully completes the 600 °C process test without the thin glass self-supporting tool Move or delamination. Disengage accompanied described above using the stripping blades and / or the Kapton ^TM tape. Process compatibility for two different PPFP films (deposited as described above) is shown in Table 3. The PPFP 1 of Example 3a was formed using C4F8/(C4F8+CF4)=0, that is, using CF4/H2 and not using C4F8, and the PPFP 2 of Example 3b was deposited using C4F8/(C4F8+CF4)=0.38. . Two types of PPFP films were preserved in a vacuum treatment test, an SRD treatment test, a 400 ° C treatment test, and a 600 ° C treatment test. However, after 20 minutes of ultrasonic cleaning of PPFP2, delamination was observed indicating insufficient adhesion to withstand such treatment. Nevertheless, the surface modification layer of PPFP2 can be applied to some applications such as where ultrasonic processing is not necessary.

In Examples 3a and 3b above, each of the carrier and the sheet was Eagle XG® glass, wherein the carrier was a 630 micron thick 150 mm diameter SMF wafer and the sheet was 100 mm squared and 100 microns thick. Due to the small thickness of the surface modifying layer, there is almost no risk of degassing, which can cause contamination of the device. In addition, because the surface modification layer does not exhibit degradation, there is an even smaller risk of degassing. In addition, as indicated in Table 3, each of the sheets was cleaned using the SC1 process prior to heat treatment at 150 ° C for one hour in a vacuum.

Other materials that can act to control the surface energy in different ways can be used as the surface modifying layer to control the room temperature bonding force and the high temperature bonding force between the sheet and the carrier. For example, a bonding surface that can produce controlled bonding can be produced by treating the glass carrier and/or glass flakes with decane. The decane is selected to produce a suitable surface energy and to have sufficient thermal stability for the application. The vehicle or thin glass to be treated can be cleaned by, for example, O2 plasma or UV-ozone, and SC1 or standard clean two (SC2, known in the art) cleaning, In order to remove organics and other impurities (eg, metals) that will interfere with the decane reacted with the surface sterol groups. Detergents based on other chemical methods, such as HF or H2SO4 washing chemistry, may also be used. The carrier or thin glass may be heated to control surface hydroxyl concentration prior to decane application (as discussed above in conjunction with the surface modifying layer of HMDS), and/or may be heated after decane application to complete decane with surface hydroxyl groups condensation. The concentration of unreacted hydroxyl groups after decaneization can be sufficiently low before blocking to prevent Permanent bonding between the thin glass and the carrier at a temperature of 400 ° C, i.e., to form a controlled bond. This method is described below.

Example 4a

The glass carrier whose surface was treated with O2 plasma and SC1 was subsequently treated with 1% dodecyltriethoxysilane (DDTS) in toluene and annealed in vacuum at 150 ° C for 1 hr to complete the condensation. . The DDTS treated surface exhibited a surface energy of 45 mJ/m ² . As shown in Table 4, a glass flake (already cleaned by SC1 and heated in vacuum at 400 ° C for one hour) was bonded to the carrier joining surface with a DDTS surface modifying layer on the carrier engaging surface. The article was preserved in the wet process test and the vacuum process test, but was not preserved in a hot process exceeding 400 ° C in the absence of bubbles formed under the carrier due to thermal decomposition of decane. This thermal decomposition is expected for all linear alkoxy groups and chloroalkyl decanes R1 _x Si(OR2) _y (Cl) _z (where x = 1 to 3 and y + z = 4-x), resulting in good thermal stability. Except for the methyl, dimethyl and trimethyldecane (x = 1 to 3, R1 = CH ₃ ) of the coating.

Example 4b

The glass carrier whose bonding surface was treated with O2 plasma and SC1 was subsequently treated with 1% 3,3,3,trifluoropropyltritheoxysilane (TFTS) in toluene and vacuumed at 150 °C. Annealed for 1 hr to complete the condensation. The TFTS treated surface exhibited a surface energy of 47 mJ/m ² . As shown in Table 4, a glass flake (which has been cleaned by SC1 and then heated in vacuum at 400 ° C for one hour) is bonded to the carrier bonding surface having a TFTS surface modifying layer on the bonding surface. The article was preserved in a vacuum process test, an SRD process test, and a 400 ° C process test without permanent bonding of the glass flakes to the glass carrier. However, the 600 ° C test produced bubbles formed under the carrier due to thermal decomposition of decane. This is not surprising due to the limited thermal stability of the propyl group. Although this sample failed due to foaming in the 600 ° C test, the material and heat treatment of this example can be used for some applications in which bubbles can be tolerated and their adverse effects, such as a reduction in surface flatness, or an increase The waviness.

Example 4c

The glass carrier whose bonding surface was treated with O2 plasma and SC1 was then treated with 1% phenyltriethoxysilane (PTS) in toluene and annealed in vacuum at 200 ° C for 1 hr to complete the condensation. The PTS treated surface exhibited a surface energy of 54 mJ/m ² . As shown in Table 4, a glass flake (which has been cleaned by SC1 and then heated in vacuum at 400 ° C for one hour) is bonded to the carrier joining surface, which has a PTS surface modifying layer. The article is preserved in a vacuum process, an SRD process, and a thermal process up to 600 ° C without the permanent bonding of the glass flakes to the glass carrier.

Example 4d

The glass carrier whose bonding surface was treated with O2 plasma and SC1 was then treated with 1% diphenyldiethoxysilane (DPDS) in toluene and annealed in vacuum at 200 ° C for 1 hr to complete the condensation. The DPDS treated surface exhibited a surface energy of 47 mJ/m ² . As shown in Table 4, a glass flake (which has been cleaned by SC1 and then heated in vacuum at 400 ° C for one hour) is bonded to the carrier joining surface, which has a DPDS surface modifying layer. The article is preserved in a vacuum test and an SRD test and in a hot process up to 600 ° C without permanent bonding of the glass flakes to the glass carrier.

Example 4e.

The glass carrier whose bonding surface was treated with O2 plasma and SC1 was then treated with 1% 4-pentafluorophenyltriethoxysilane (PFPTS) in toluene and annealed in vacuum at 200 ° C for 1 hr. Complete condensation. The PFPTS treated surface exhibited a surface energy of 57 mJ/m ² . As shown in Table 4, a glass flake (which has been cleaned by SC1 and then heated in vacuum at 400 ° C for one hour) is bonded to the carrier joining surface, which has a PFPTS surface modifying layer. The article is preserved in a vacuum test and an SRD test and in a hot process up to 600 ° C without permanent bonding of the glass flakes to the glass carrier.

In Examples 4a through 4e above, each of the carrier and the sheet was Eagle XG® glass, wherein the carrier was a 630 micron thick 150 mm diameter SMF wafer and the sheet was 100 mm square by 100 microns thick. The decane layer is a self-assembled monolayer (SAM) and is therefore approximately less than about 2 nm thick. In the above examples, the SAM was produced using an organic decane having an aryl or alkyl non-polar tail and a mono-, di- or tri-alkoxide head group. Such decane and The surface of the sterol on the glass reacts to directly attach the organic functional groups. The weaker interaction between the non-polar head groups organizes the organic layer. Due to the small thickness of the surface modifying layer, there is almost no risk of degassing, which can cause contamination of the device. In addition, because the surface modifying layers do not exhibit degradation in Examples 4c, 4d, and 4e, there is an even less risk of outgassing. In addition, as indicated in Table 4, each of the glass flakes was cleaned using the SC1 process prior to heat treatment at 400 ° C for one hour in a vacuum.

As can be seen from the comparison of Examples 4a-4e, controlling the surface energy of the bonding surface to above 40 mJ/m ^{2 in} order to facilitate initial room temperature bonding is not the only consideration for producing a controlled joint that is resistant to FPD processing and still allows The sheet is removed from the carrier without damage. Specifically, as seen from Examples 4a-4e, each carrier has a surface energy of greater than 40 mJ/m ² to facilitate initial room temperature bonding for preservation of the article in vacuum processing and SRD processing. However, Examples 4a and 4b did not successfully complete the 600 ° C treatment test. As noted above, for some applications, it is also important to join: at most high temperatures (for example, 400 ° C, 500 ° C or 600 ° C, up to 650 ° C, as appropriate for the process in which the article is designed for use in the process, and the bond is not degraded to a point where it is insufficient to hold the sheet and the carrier together, The covalent bonding that occurs at these elevated temperatures is also controlled so that there is no permanent bond between the sheet and the carrier. As shown by the examples in Table 4, aromatic decane, especially phenyl decane, is suitable for providing a controlled bond that will promote initial room temperature bonding and will withstand FPD processing and still allow for sheet self-loading Remove without damage.

Fluorocarbon surface modification layer and its treatment

Another example of using a plasma polymeric film to adjust the surface energy of the bonding surface and creating a surrogate polar bonding site on the bonding surface is the deposition of a mixture of surface modifying layer films from a fluorocarbon gas source, and then by use Various methods form a nitrogen-based polar group on the surface modifying layer.

The surface modifying layer can be formed by plasma polymerization of various mixtures of fluorocarbon gas sources to provide various surface energies, including surface energies greater than about 50 mJ/m ² , such as by fitting by S. Wu (1971) A theoretical model developed for the contact angle (CA) of three different test liquids (deionized water (water), hexadecane (HD) and di-iodomethane (DIM) in this case) Calculation (Reference: S. Wu, J. Polym. Sci. C, 34, 19, 1971, hereinafter referred to as "Wu model"). The surface energy of the carrier on the joint surface is greater than about 50 mJ/m ² . Bonding to a thin glass sheet is beneficial because it facilitates initial room temperature bonding of the carrier to the thin glass sheet and allows for FPD processing of the carrier/thin glass sheet without its disengagement during processing. In some cases, Depending on the surface modifying layer composition and deposition conditions, the surface modifying layer having this surface energy can allow debonding by stripping, even at temperatures up to about 600 ° C and in some cases even higher. And after the thin glass sheet. In general, the source gas includes etching gas and polymerization. A mixture of gases is formed. As discussed above in connection with Figure 5, the etching gas may be CF4 and the polymer forming gas may be C4F8. Alternatively, as shown in Figure 13, the etching gas may be CF4, and the polymer forming gas may be CHF3. As shown in both Figures 5 and 13, in general, the lower the percentage of polymer forming gas, the higher the total surface energy 502, 1312 of the resulting joint surface, wherein the total surface energy is the polar component 504. a combination of 1314 (triangular data points) and dispersed components 506, 1316 (square data points). The percentage of polymer forming gas (eg, CHF3) during plasma polymerization can be controlled in a similar manner by using an inert gas such as Ar. To control the resulting surface energy, as shown in Figure 13A, the graph shows the total surface energy in mJ/m2. Although not wishing to be bound by theory, the inert gas can act as an etchant, diluent, or both. In any case, it is obvious that the surface energy of the carrier glass can be modified without any CF4 in the gas stream by separate CHF3. The deposition of the surface modification layer can occur at atmospheric pressure or reduced pressure, and electricity is utilized. Excited to perform, the plasma is excited, for example, by DC or RF parallel plates, inductively coupled plasma (ICP), electron cyclotron resonance (ECR), downstream microwave or RF plasma. The plasma polymerization surface modification layer can be placed on the carrier, On the flakes or both. As indicated above in connection with the examples in Table 3, the plasma polymerization produces a layer of highly crosslinked material. Control of the reaction conditions and source gases can be used to control the thickness, density and chemical properties of the surface modifying layer. It is specially formulated for the functional groups to be applied. Moreover, by controlling the properties of the film, the surface energy of the carrier bonding surface can be adjusted. However, surface energy is one of the considerations in controlling the degree of bonding.

The degree of controlled engagement or moderate engagement can additionally be adjusted by controlling the polarity engagement to achieve the desired surface energy. One way to control the polarity bonding is to expose the surface modifying layer (formed as above) to another process to incorporate a polar group, such as by treatment with a nitrogen-containing plasma. This treatment increases the adhesion based on the formation of a thin surface modifying layer via a nitrogen based polar functional. The nitrogen-based polar group formed during subsequent processing does not condense with the sterol group to cause permanent covalent bonding, and thus can control the sheet and the carrier during subsequent processing to perform placement of the film or structure on the sheet The degree of engagement between. Methods of forming nitrogen-based polar groups include, for example, nitrogen plasma treatment (examples) 5b-d, k, l), ammonia plasma treatment (Examples 5e, f, h-j), and nitrogen/hydrogen plasma treatment (Example 5m).

It was observed that the thin glass piece and the glass carrier bonded to the surface modification layer treated with the nitrogen-containing plasma were not permanently adhered after annealing at 600 ° C, that is, they successfully completed the portion (c) of the 600 ° C temperature test. In addition, this modest joint is strong enough to be preserved in FPD processing (including vacuum test (1), wet process test (2) and ultrasonic test (5), and can be removed by application of sufficient peel force Engage. Debonding allows removal of the device fabricated on the thin glass and reuse of the carrier. Nitrogen plasma treatment of the surface modifying layer can achieve one or more of the following advantages: high surface energy and low water contact angle, which results in strong adhesion between the sheet and the carrier after initial bonding, with minimal bubble defects ( See Examples 5b-f and il); reduction in defect formation during heat treatment due to improved thermal stability of the surface modification layer (Examples 5c, 5d, 5k, 5l, ie, samples treated with N2 exhibit reduced Bubble formation, as visually observed; and/or easier process window, because the separation of the surface modification layer, its formation and processing allow for different process optimization of the carrier/surface modification layer and surface modification. Layer/thin glass interface (Examples 5b-f and hm). That is, the base material of the surface modifying layer and its own deposition process can be formulated to optimize the interaction between the surface modifying layer and the carrier bonding surface. Subsequently, independently, after deposition of the surface modifying layer on the carrier, the properties of the surface modifying layer can be modified by processing to optimize the surface modifying layer and the sheet to be placed thereon. interaction.

In the examples of Table 5 below, various conditions were used to deposit a plasma polymeric film onto a glass carrier. The glass carrier is a substrate made of Corning® Eagle XG® aluminoborosilicate free alkali metal display glass (available from Corning Incorporated, Corning NY). The SC1 and/or SC2 chemistry and standard cleaning techniques are used to clean the vehicle prior to deposition of the surface modifying layer. The film was deposited in an Oxford Plasmalab 380 Inductively Coupled Plasma (ICP) system with a 13.56 MHz RF source on both the coil and the platform, with the platform temperature fixed at 30C. Nitrogen and ammonia plasma treatment for the surface modification layer of samples 5a-5j is performed in an STS multiplex PECVD apparatus (available from SPTS, Newport, UK) having a triode electrode configuration mode in which the carrier is placed Placed on a platform heated to 200 C, a specified wattage of 380 kHz RF energy is applied to the platform, with a showerhead placed over the platform to apply a specified wattage of 13.5 MHz RF energy to the showerhead. For the energy applied to both Oxford ICP and STS PECVD, the value is shown as #/#W, where the value before the slash is the watt applied to the top electrode (coil on ICP or sprinkler on PECVD) The number, and the value after the slash, is the wattage applied to the platform. In the case where only one value is shown, this value is for the top electrode. The flow rate of gas into the chamber is shown in Table 5 (flow rate is calculated as the standard cubic centimeter per minute - sccm). Thus, for example, the notation for Example 5g in the "Surface Treatment" column of Table 5 is interpreted as follows: in an Oxford ICP apparatus, 30 sccm of CF4, 10 sccm of C4F8, and 20 sccm of H2 are flowed together into a chamber having a pressure of 5 mTorr; 1000 W of 13.5 MHz RF energy was applied to the coil, and 50 W of 13.56 MHz RF energy was applied to the 30C platform on which the carrier was placed; and the deposition time was 60 seconds. The notation of the remaining instances in the surface treatment column can be interpreted in a similar manner. As another example, in the "plasma processing" column, the notation for the treatment in Example 5h is interpreted as follows: After the surface modifying layer is formed according to the parameters in the surface treatment column of Example 5h, then 100 sccm of NH3 is supplied to have An STS PECVD chamber with a pressure of 1 Torr and a temperature of 200 ° C; 13.56 MHz of 100 W was applied to the shower head; and treatment was carried out for 30 seconds. The notation for the remaining instances in the "plasma processing" column can be interpreted in a similar manner. The surface energy, ie the polar component and the dispersion component, are fitted to the contact angles suitable for three different test liquids (in this case deionized water (water), hexadecane (HD) and diiodomethane (DIM)) ( The Wu model of CA) is calculated in mJ/m ² (millijoules per square meter). For surface energy, the polar component (P) and the dispersed component (D), as well as the total energy (T), are shown.

In Examples 5b-5f and 5h-5l of Table 5, nitrogen-based polar groups are formed on the surface modifying layer, wherein the polar groups are in the carrier and the sheet (eg, glass carrier and glass sheet) Moderate adhesion to create a temporary connection The temporary joint is strong enough to be preserved in the FPD process, but weak enough to allow disengagement. After the treatment, the concentration of the polar group on the surface of the surface modifying layer is greater than the concentration of the polar group in the bulk of the surface modifying layer.

Examples of treatment with NH3 plasma (5e, f and h-j).

In the ICP plasma system, a moderate surface energy SML (Comparative Example 5a) was deposited from 30 sccm CF4, 10 sccm C4F8, 20 sccm H2 at 1500 W coil and 50 W platform RF power at 5 mT, and 1000 W coil and 50 W platform RF power were used at 5 mT. Another moderate surface energy SML (Comparative Example 5g) was deposited from 30 sccm CF4, 10 sccm C4F8, 20 sccm H2. The surface energy of the untreated fluoropolymer film is shown in Table 5. Samples were transferred to an STS PECVD system and exposed to ammonia plasma using the conditions listed in Table 5 (Examples 5e, 5f, 5h-j). The surface tension as measured by the Wu equation using DI water and hexadecane is increased from about 40 mJ/m2 to about 65-80 mJ/m2 depending on the ammonia plasma condition. A thin glass piece was bonded to each of these NH3 plasma modified samples. After the temperature test at 600 ° C, it was visually observed that there was almost no change in the bubble region (the formal degassing test was not performed), and the thin glass sheets in all of these samples were easily debonded by hand.

Example (5c, d, k, l) treated by N2 plasma.

In the ICP plasma system, a moderate surface energy SML (Comparative Example 5a) was deposited from 30 sccm CF4, 10 sccm C4F8, 20 sccm H2 at 1500 W coil and 50 W platform RF power at 5 mT, and 1000 W coil and 50 W platform RF power were used at 5 mT. Another moderate surface energy SML (Comparative Example 5g) was deposited from 30 sccm CF4, 10 sccm C4F8, 20 sccm H2. The surface energy of the untreated fluoropolymer film is shown in Table 5. In the ICP system Samples 5c, d, k, and l were subjected to N2 plasma in-situ treatment using the conditions listed in Table 5. The surface energy increases from about 40 mJ/m2 to over 70 mJ/m2 depending on the plasma conditions. A thin glass piece is bonded to each of these samples. The thin glass sheets of all samples were easily debonded by hand after testing at 600 °C.

An example (5m) of simultaneous treatment with N2 and H2 plasma.

In the ICP plasma system, moderate surface energy SML (Comparative Example 5g) was deposited from 30 sccm CF4, 10 sccm C4F8, 20 sccm H2 using a 1000 W coil and a 50 W platform RF power at 5 mT. The surface tension of the untreated fluoropolymer film is shown in Table 5. Sample 5m was subjected to simultaneous N2+H2 plasma in-situ treatment in the ICP system using the conditions listed in Table 5. The surface energy different from the untreated fluoropolymer film was not exhibited.

Example (5b) by treatment of sequential N2 and H2 plasmas.

In the ICP plasma system, moderate surface energy SML (Comparative Example 5a) was deposited from 30 sccm CF4, 10 sccm C4F8, 20 sccm H2 at 1500 W coil and 50 W platform RF power at 5 mT. The surface energy of the untreated fluoropolymer film is shown in Table 5. This sample was then subjected to sequential N2 and H2 plasma in-situ treatment in the ICP system using the conditions listed in Table 5. The surface energy is increased to over 70 mJ/m2. This value is similar to the value obtained with ammonia plasma or nitrogen plasma. A thin glass piece was bonded to the sample and subjected to a 600 ° C temperature test, after which the thin glass piece was debonded from the carrier, that is, the sample successfully completed part (c) of the 600 ° C treatment test.

The XPS data reveals the effects of ammonia plasma treatment and nitrogen plasma treatment on the surface modification layer. In particular, ammonia plasma treatment roughly halved the surface modified carbon content and reduced the fluorine concentration by about a quarter and increased by about 0.4 at% nitrogen. Can also See increased enthalpy, oxygen, and other glass components, which removes the fluoropolymer from the ammonia plasma while increasing the small amount of nitrogen to the surface. Nitrogen plasma treatment increases the nitrogen content to 2 at% and is similar to ammonia to reduce the carbon content and fluorine content. Niobium, oxygen and other glass components are also increased, which is consistent with a reduction in film thickness. Therefore, it was confirmed that the ammonia plasma treatment and the nitrogen plasma treatment added a polar group to the surface modification layer, and the surface layer thickness was reduced. The resulting thickness of the surface modifying layer is typically less than 20 nm. Thus, the effective surface modifying layer will typically balance the surface modifying layer thickness with subsequent surface treatment time to achieve a controlled bond.

The thin glass sheet bonded to the carrier according to the example of Table 5 as described above is a substrate made of Corning® Willow® glass, which is an aluminoborosilicate-free alkali metal glass (available from Corning Incorporated, Corning NY). And has a thickness of 100, 130 and 150 microns. Prior to bonding, the Willow® glass is cleaned using oxygen plasma followed by SC1 and/or SC2 chemistry and standard cleaning techniques.

In the example of Table 5, although the joint surface on which the surface modifying layer is disposed is glass, it is not necessary to be in this case. Alternatively, the bonding surface can be another suitable material having surface energy and properties similar to glass, such as germanium, polycrystalline germanium, single crystal germanium, ceramic, glass-ceramic, sapphire or quartz.

It is demonstrated in the examples of Tables 3 and 5 that the use of a plasma-polymerized fluoropolymer surface modifying layer of less than 20 nm thickness controls the bonding energy of the glass bonding surface. The initial engagement of the glass sheet with such a glass carrier having a surface modifying layer thereon is similar to joining the glass to the glass: the front end of the joint moves rapidly due to the strong mutual attraction between the sheet and the coated glass carrier. This mutual attraction is due to the thin glass in the presence or absence of hydrogen-bonded molecular water. The on-chip polar group (almost sterol group) interacts with the dipole-dipole (Keesom) between the polar groups on the surface modifying layer of the carrier. However, the fluoropolymer surface modification treatment prevents permanent bonding of the sheet to the carrier at temperatures up to 600 ° C with respect to device fabrication. In order to provide a mandatory cost advantage for low-volume acid thinning of thicker glass, the carrier must be reusable. This is a concern when using a fluorinated surface modifying layer because the fluoropolymer deposition process etches the surface of the carrier. Although the surface modification layer has been used to demonstrate repeated use of the carrier, the surface roughness has increased from 0.3 nm to about 1.2 nm Ra. Such an increase in roughness can affect vehicle reusability by limiting the joint area to reduce joint energy (joining energy on the vehicle that has been reused after deposition, removal, and redeposition of the surface modifying layer). In addition, the increase in surface roughness may limit the reuse of carriers in other applications, such as the use of the carrier itself as a display substrate, due to non-compliance with specifications for the roughness of the introduced glass. It has also been observed that roughness is induced on the joined surface side of the thin glass sheet after annealing a pair of bonded thin glass sheets and the carrier at a temperature of >300 °C. The increased roughness on the sheet bonding surface may be due to the etching of the thin glass bonding surface by the desorption of fluorine-containing gas from the carrier bonding surface of the surface modifying layer. In some cases, such an increase in the roughness of the joint surface is not continuous. In other cases, although the increase in roughness is small, such an increase may be unacceptable because it may limit, for example, repeated use of the vehicle. Additionally, there may be reasons for the undesirable use of fluorinated gases in certain manufacturing operations, such as health and safety.

Thus, there may be situations in which it is desirable to use an alternative polar bond to generate sufficient surface energy (eg, >50 mJ/m ² as discussed above in connection with the examples in Table 5) for producing a controlled bond, That is, it is strong enough to be preserved in the FPD process, but allows the sheet to be separated from the carrier without damage (even after high temperature processing, such as after treatment at 400 ° C or higher or 600 ° C or higher). Accordingly, the inventors explore alternative ways to form suitable polar joints that can be used for controlled engagement of the sheet with the carrier.

The inventors have discovered that the use of a hydrocarbon polymer or, more typically, a carbonaceous layer would be available to etch the glass, with little or no fluorine. However, several key challenges must be overcome. For the carbonaceous layer to be joined to the glass, the surface energy of the carbonaceous layer should be greater than about 50 mJ/m ² . In order to provide a bond that is strong enough to be preserved in a wet process without liquid immersion between the sheet and the carrier, in some cases, the carbonaceous surface modifying layer should have a surface energy of 65 mJ/m2 or higher. At 65 mJ/m2, the surface energy of the carrier (for bonding to a thin glass sheet) is sufficient to prevent liquid (eg, water) from penetrating between the carrier and the sheet during subsequent processing. With a surface energy of about 50 mJ/m2, bonding to a thin glass sheet may be sufficient for most FPD treatments, but heat treatment may be required to prevent liquid infiltration. Specifically, the polar component of the hydrocarbon layer must be increased in order to achieve a strong dipole-dipole junction directly mediated by the sterol group of the thin glass sheet or by hydrogen bonding molecule water. The carbonaceous layer should also exhibit thermal, chemical, and vacuum compatibility so that it will be suitable for use in a carrier-sheet article that will undergo at least an amorphous silicon (aSi) TFT, a color filter (CF), or Capacitive touch device manufacturing process. This seems to be possible because aliphatic hydrocarbons such as polyethylene exhibit great thermal stability in an inert atmosphere. Unlike fluoropolymers which can be depolymerized in some cases, HDPE is only charred. Although HDPE can be charred, if the thickness of the polymer is sufficiently low, it can still be viewed through it. The last concern is that mechanical stability and wet process compatibility seem to require a higher adhesion than can be achieved with a single van der Waals force. It will be appreciated that a bonding energy of from about 250 mJ/m2 to about 275 mJ/m2 is beneficial in the case of using glass flakes for preservation in wet ultrasonic processing. This large bonding energy can be attributed to particle and edge defects, rather than the basic requirements of the bonding process. Under optimal bonding, the two clean glass surfaces can produce an engagement energy of about 150 mJ/m2. Some covalent bonding is required to achieve a bond strength of 250-275 mJ/m2.

The surface modifying layer probed in the examples of Tables 6-12 is an organic surface modifying layer based on a fluorine-free underlying material. As will be described in more detail below, an amorphous hydrocarbon layer (or just a carbonaceous layer) can be produced on the glass carrier (Table 6), but the surface energy is not generated on the clean glass surface for preservation in the FPD process. Adhesive enough. This is not surprising since the organic surface modifying layer based on methane and hydrogen does not contain strong polar groups. To increase the polar groups available for bonding to thin glass sheets, additional gas is added during plasma polymerization and sufficient surface energy is achieved (Table 7). However, while sufficient surface energy can be achieved under some conditions, this one-step process involves a certain amount of complexity in obtaining an appropriate mixture of source materials. Therefore, a two-step process is developed in which: in the first step, a surface modifying layer is formed (for example, similar to the manner in which the step is performed in the example of Table 6, formed from two gases); then, in the second step The surface modifying layer is treated in a variety of ways to increase the surface energy and polar groups available for bonding to the thin glass sheet. Despite the more steps, this process is less complicated for management to achieve desirable results. The treatment increases the polar groups that will bond to the surface of the surface modifying layer of the sheet. Thus, polar groups can be utilized to bond the carbonaceous layer to the flakes, although the bulk of the surface modifying layer can in some cases not contain polar groups. At Various ways of modifying the initial surface modifying layer are explored in the examples of Tables 8-12, wherein: in the example of Table 8, the surface modifying layer is treated with NH3; in the example of Table 9, the surface modifying layer is treated with N2. In the example of Table 10, the surface modifying layer was treated sequentially with N2 followed by H2; in the example of Table 11, the surface modifying layer was treated sequentially with N2-O2 and then with N2; in the example of Table 12, N2 was used. -O2 treatment of the surface modifying layer; and in an alternative example after Table 12, the surface modifying layer was treated with O2 alone. These examples show the use of nitrogen and oxygen polar groups, although other polar groups may be possible.

Forming a carbonaceous surface modifying layer using a hydrocarbon (eg, methane CH4) and optionally hydrogen (eg, H2)

Another example of using a plasma polymer film to adjust the surface energy of the bonding surface and covering the surface hydroxyl groups on the bonding surface is the deposition of a surface modifying layer film from a carbonaceous gas (eg, a hydrocarbon gas such as methane) in plasma polymerization. Use with another gas (eg, hydrogen H2) as needed. However, in most cases, hydrogen flow is preferred because in other cases, the deposited material tends to be graphite, dark, and has a low energy band gap. This point is the same in all of the carbonaceous surface modifying layers of Tables 6-12 and 16. The surface modifying layer can be formed at atmospheric or reduced pressure and is performed using plasma excitation, such as DC or RF parallel plates, inductively coupled plasma (ICP), electron cyclotron resonance (ECR), downstream microwaves, or RF plasma. The plasma polymerized surface modifying layer can be disposed on a carrier, a sheet, or both. As indicated above in connection with the examples of Table 3, plasma polymerization produces a layer of highly crosslinked material. Control of the reaction conditions and source gases can be used to control the thickness, density and chemical properties of the surface modifying layer, tailored to the functional groups to be applied, and by controlling the properties of the film, the surface energy of the bonding surface The amount can be adjusted. The surface energy can be adjusted to control the extent of the joint, i.e., to prevent permanent covalent bonding between the sheet and the carrier during subsequent processing to effect placement of the film or structure on the sheet.

In the examples of Table 6 below, various conditions were used to deposit a plasma polymeric film onto a glass carrier. The deposition parameters explored in the examples in Table 6 are: gas ratio (methane: hydrogen); pressure, ICP coil and RF bias power. The glass carrier is a substrate made of Corning® Eagle XG® aluminoborosilicate free alkali metal display glass (available from Corning Incorporated, Corning NY). The vehicle is cleaned using SC1 and/or SC2 chemistry and standard cleaning techniques prior to film deposition. A film was deposited in an Oxford Plasmalab 380 ICP (available from Oxford Instruments, Oxfordshire UK) inductively coupled plasma (ICP) tools, where the carrier was placed on a platform with a specified wattage (in the "RF bias" column) The 13.56 MHz RF energy is applied to the platform, with coils placed above the platform, and 13.5 MHz RF energy of a specified wattage (indicated in the "Coil" column) is applied to the coil. The flow rates of the methane source (CH4) and the hydrogen source (H2) into the chamber are shown in the columns of CH4 and H2, respectively (the flow rate is calculated as the standard cubic centimeter per minute - sccm). The CH4 and H2 gases are allowed to flow together. The ratio of H2:CH4 source gas is also shown in the "H2/CH4" column, and the pressure in the chamber (in mTorr) is shown in the "Pressure" column. Thus, for example, the notation for Example 6a in Table 6 is interpreted as follows: In an Oxford ICP apparatus, 6.7 sccm of CH4 and 33.3 sccm of H2 are flowed together into a chamber having a pressure of 20 mTorr; 1500 W of 13.5 MHz RF energy is applied. The coil is placed and 300 W of 13.56 MHz RF energy is applied to the platform on which the carrier is placed. The platform temperature was 30C for all depositions. The notation of the remaining instances can be interpreted in a similar manner. The surface energy is obtained by using three different test liquids (in this case, deionized water (shown in column "W"), hexadecane (shown in column "H"), and diiodomethane (column "DIM"). The contact angle (CA) and the Wu model shown in )) are calculated in mJ/m ² (millijoules per square meter). For surface energy, the polar component (P) and the dispersed component (D), as well as the total energy (T), are shown.

The surface energies of Examples 6a-6j varied from about 40 mJ/m ² to about 50 mJ/m ² . Basically, however, the surface energies of these examples are less than about 50 mJ/m ² (considered to be suitable for controllably bonding glass carriers to glass flakes). The thickness of the surface modifying layer is about 6 nm. These examples do not result in sufficient adhesion between the carrier and the thin glass sheet to be preserved in the FPD process, that is, the carrier and the thin glass sheet are observed to foam during the vacuum test and during the wet process test. It was observed to have hot water infiltration.

Although such surface modifying layers are not themselves suitable for bonding to thin glass sheets, they can be used in other applications, such as applying polymer sheets to glass carriers for processing electronic or other structures to thin polymer sheets. On the material, as discussed below. Alternatively, the sheet can be a composite sheet having a polymeric surface that can be bonded to a glass carrier. In this case, the composite sheet A layer of glass may be included on which electrons or other structures may be disposed, while the polymeric portion forms an engaging surface for controlled engagement with the glass carrier.

In the example of Table 6, although the joint surface on which the surface modifying layer is disposed is glass, it is not necessary to be in this case. Alternatively, the bonding surface can be another suitable material having surface energy and properties similar to glass, such as germanium, polycrystalline germanium, single crystal germanium, ceramic, glass-ceramic, sapphire or quartz.

Single step formation of a surface modifying layer using a mixture of non-fluorinated sources

Another example of using a plasma polymeric film to adjust the surface energy of the bonding surface and covering the surface hydroxyl groups on the bonding surface is the deposition of a surface modifying layer film from a mixture of non-fluorinated gas sources, including carbonaceous gases, such as hydrocarbons. Deposition of the surface modifying layer can occur at atmospheric or reduced pressure and is performed using plasma excitation, such as DC or RF parallel plates, inductively coupled plasma (ICP), electron cyclotron resonance (ECR), downstream Microwave or RF plasma. The plasma polymerized surface modifying layer can be disposed on a carrier, a sheet, or both. As indicated above in connection with the examples of Table 3, plasma polymerization produces a layer of highly crosslinked material. Control of the reaction conditions and source gases can be used to control the thickness, density, and chemistry of the surface modifying layer to tailor the functional groups for the desired application, and by controlling the properties of the film, the surface energy of the bonding surface can be adjusted. The surface energy can be adjusted to control the extent of the joint, i.e., to prevent permanent covalent bonding between the sheet and the carrier during subsequent processing to effect placement of the film or structure on the sheet.

In the examples of Table 7 below, various conditions were used to deposit a plasma polymeric film onto a glass carrier. The glass carrier is a substrate made of Corning® Eagle XG® aluminoborosilicate free alkali metal display glass (available from Corning Incorporated, Corning NY). The vehicle is cleaned using SC1 and/or SC2 chemistry and standard cleaning techniques prior to film deposition. Deposited in an Inductively Coupled Plasma (ICP) configuration mode on an Oxford Plasmalab 380 ICP (available from Oxford Instruments, Oxfordshire UK) where the carrier is placed on the platform and the wattage is specified (in the RF Offset column) The 13.56 MHz RF energy indicated in the ) is applied to the platform, with coils placed above the platform, and 13.5 MHz RF energy of a specified wattage (indicated in the "Coil" column) is applied to the coil. The flow rates of methane (CH4), nitrogen (N2) and hydrogen (H2) source gases into the chamber are shown in columns CH4, N2 and H2, respectively (flow rate is the standard cubic centimeter per minute - sccm) . The CH4, N2 and H2 gases are allowed to flow together. The ratio of N2:CH4 source gas is also shown in the "N2/CH4" column, and the pressure in the chamber (in mTorr) is shown in the "Pressure" column. Thus, for example, the notation for Example 7g in Table 7 is interpreted as follows: In an Oxford 380 ICP apparatus, 15.4 sccm of CH4, 3.8 sccm of N2, and 30.8 sccm of H2 were flowed together into a chamber having a pressure of 5 mTorr; 13.5 MHz RF energy is applied to the showerhead; and 50 W of 13.56 MHz RF energy is applied to the platform on which the carrier is placed. For all of the samples in Table 7, the platform temperature was 30C. The notation of the remaining instances can be interpreted in a similar manner. The surface energy is obtained by using three different test liquids (in this case, deionized water (shown in column "W"), hexadecane (shown in column "H"), and diiodomethane (column "DIM"). The contact angle (CA) and the Wu model shown in )) are calculated in mJ/m ² (millijoules per square meter). For surface energy, the polar component (P) and the dispersed component (D), as well as the total energy (T), are shown. In addition, the "Thickness" column shows the thickness value (in angstroms) of the surface modifying layer deposited according to the conditions indicated for the particular example.

Example 7a shows a surface modifying layer made of methane alone. Under these deposition conditions, the surface modifying layer formed by methane achieves a surface energy of only about 44 mJ/m ² on the carrier. Although it is not at the level required for glass to glass controlled bonding, it can be adapted to bond a polymeric bonding surface to a glass carrier.

Examples 7b through 7e show surface modifying layers made from plasma polymerization of methane and nitrogen at various ratios of N2:CH4. Under these deposition conditions, the methane-nitrogen formed surface modifying layer achieved a surface energy of about 61 mJ/m ² (Example 7e) to about 64 mJ/m ² (Example 7d) on the carrier. These surface energies are sufficient to controllably bond the thin glass sheet to the glass carrier.

Example 7f shows a surface modifying layer made from a plasma polymerization of methane and hydrogen (H2). Under these deposition conditions, the methane-hydrogen formed surface modifying layer achieves a surface energy of about 60 mJ/m ² on the carrier that is sufficient to controllably bond the thin glass sheet to the glass carrier.

Examples 7g through 7j show surface modifying layers made from plasma polymerization of methane, nitrogen and hydrogen. Under these deposition conditions, the methane-nitrogen-hydrogen formed surface modifying layer achieves a surface energy of about 58 mJ/m ² (Example 7 g) to about 67 mJ/m ² (Example 7j) on the carrier, which surface energy is sufficient A thin glass sheet is controllably bonded to the glass carrier.

It was observed that the thin glass sheets and the carrier having the surface modifying layer formed according to Examples 7b to 7j were not permanently adhered after annealing at 450 ° C, that is, they successfully completed the portion (c) of the 400 ° C temperature test. Debonding allows removal of the device fabricated on the thin glass and reuse of the carrier.

The thin glass sheets bonded to each of the carriers according to the examples (7b to 7j) of Table 7 are substrates made of Corning® Willow® glass, which is an aluminoborosilicate-free alkali-free glass (available) From Corning Incorporated, Corning NY) and having a thickness of 100, 130 and 150 microns. Prior to bonding, the Willow® glass is cleaned using oxygen plasma followed by SC1 and/or SC2 chemistry and standard cleaning techniques.

In the example of Table 7, although the joint surface on which the surface modifying layer is disposed is glass, it is not necessary to be in this case. Alternatively, the bonding surface can be another suitable material having surface energy and properties similar to glass, such as germanium, polycrystalline germanium, single crystal germanium, ceramic, glass-ceramic, sapphire or quartz.

The surface modifying layer of the example of Table 7 was formed in a single step process. That is, proper surface energy and polar groups are achieved by depositing a surface modifying layer from a selected mixture of gases under appropriate conditions. Despite the appropriate gas and Conditions, but the process involves a certain amount of complexity in achieving the proper gas mixture. Therefore, looking for a simpler process. Assuming proper surface energy and appropriate polar groups can be achieved in a two-step process, each step will be simple and stable. Specifically, it is assumed that in the first step, the carbonaceous surface modifying layer will be deposited, and in the second step, the surface modifying layer will be treated to increase the surface energy and produce the appropriate polar groups for controlled bonding. Where the polar group may be more concentrated at the surface of the surface modifying layer to be bonded to the sheet without the polar groups being in the bulk material. According to the example of Table 6, it is known that the pressure and coil power have the greatest influence on the surface energy. In addition, it is known that the thickness of the film appears to increase as the bias increases and the pressure decreases. Therefore, based on these results, for further exploration of the process for increasing surface energy and incorporating polar groups, the starting point is: 20sccm CH4 40sccm H2 5mT 1500/50W 60s amorphous hydrocarbon polymer A surface modification layer deposition process that produces a carbonaceous surface modifying layer having a thickness of about 6.5 nm. For the base surface modifying layer, various treatments are performed in the second step, as set forth in the examples of Tables 8-11, in order to modify the polar groups at the surface of the surface modifying layer of the sheet to be bonded and concentration. Although specific examples of starting materials and processing materials for the surface modifying layer are discussed below, typically, the carbonaceous layer is formed from a carbonaceous source and the polar groups are subsequently added by subsequent processing. Similarly, although specific polar groups are shown by way of example, other polar groups may be possible.

Polar groups are introduced into the carbonaceous surface modifying layer by NH3 treatment

Another example of using a plasma polymeric film to adjust the surface energy of the bonding surface and creating a surrogate polar bonding site on the bonding surface is a thin surface modifying layer film from a carbon source (eg, methane (carbonaceous gas source)) and Deposition from hydrogen H2, followed by Nitrogen treatment of the surface reforming layer that has just been formed. Nitrogen treatment can be performed using, for example, ammonia plasma treatment. Deposition of the surface modifying layer can occur at atmospheric or reduced pressure and is performed using plasma excitation, such as DC or RF parallel plates, inductively coupled plasma (ICP), electron cyclotron resonance (ECR), downstream Microwave or RF plasma. The plasma polymerized surface modifying layer can be disposed on a carrier, a sheet, or both. As indicated above in connection with the examples of Table 3, plasma polymerization produces a layer of highly crosslinked material. Control of the reaction conditions and source gases can be used to control film thickness, density, and chemistry to tailor the functional groups to be used, and by controlling the properties of the film, the surface energy of the bonding surface can be adjusted. The nitrogen-based polar group formed during subsequent ammonia plasma treatment does not condense with the sterol group to cause permanent covalent bonding, and thus can be controlled during subsequent processing to place the film or structure on the sheet. The degree of engagement with the carrier.

In the examples of Table 8 below, various conditions were used to deposit a plasma polymerized surface modifying layer film onto a glass carrier. The glass carrier is a substrate made of Corning® Eagle XG® aluminoborosilicate free alkali metal display glass (available from Corning Incorporated, Corning NY). The vehicle is cleaned using SC1 and/or SC2 chemistry and standard cleaning techniques prior to film deposition. The surface treatment was deposited in an Inductively Coupled Plasma (ICP) configuration mode in an Oxford Plasmalab 380 ICP (available from Oxford Instruments, Oxfordshire UK) with the carrier placed on the platform to apply a specified wattage of 13.56 MHz RF energy. On the platform, a coil is placed over the platform, and a 13.5 MHz RF energy of a specified wattage is applied to the coil. For the application of energy, more generally, the value is shown as #/#W, where the value before the slash is the wattage applied to the coil (spray head), and the value after the slash is the wattage applied to the platform. In the case where only one value is displayed, this value is for the coil. The flow rate of gas into the chamber is shown in Table 8 (flow rate is calculated as the standard cubic centimeter per minute - sccm). During the plasma treatment of the surface modification layer (SML), the temperature of the chamber was 30 °C. Thus, for example, the notation for Example 8a in the "Surface Treatment" column of Table 8 is as follows: In an Oxford ICP device, 40 sccm of CH4 is flowed into a chamber having a pressure of 5 mTorr; 1500 W of 13.5 MHz RF energy is applied to Sprinkler; 50 W of 13.56 MHz RF energy was applied to the platform on which the carrier was placed; the chamber was at a temperature of 30 ° C; and the deposition time was 60 seconds. The notation of the remaining instances in the surface treatment column can be interpreted in a similar manner, with the exception that the surface treatment is performed in STS multiplex PECVD (available from SPTS, Newport, UK). The carrier was placed on a ground electrode maintained at 200 C and the gas was introduced via a 13.56 MHz RF driven showerhead. As another example, in the "plasma processing" column, the notation for the treatment in Example 8a is interpreted as follows: After the surface modifying layer is formed according to the parameters in the surface treatment column of Example 8a, then 100 sccm of NH3 is supplied to have A chamber with a pressure of 1 Torr and a temperature of 200 ° C; a 300 W of 13.56 MHz RF was applied to the shower head and treated for 60 seconds. The notation for the remaining instances in the "plasma processing" column can be interpreted in a similar manner. The surface energy is obtained by using three different test liquids (in this case, deionized water, hexadecane (H) and diiodomethane (DIM)) and the Wu model, in mJ/m ² (mJ/m ^{2 )} Square meter) to calculate. For surface energy, the polar component (P) and the dispersed component (D), as well as the total energy (T), are shown.

Examples 8a and 8b show a plasma polymerized hydrocarbon surface upgrading layer which is subsequently treated with a nitrogen containing gas (ammonia). In the case of Example 8a, ammonia itself used 300 W of power, while in Example 8b, ammonia was diluted with hydrazine and polymerized at a lower power of 50 W. However, in each case, sufficient surface energy is obtained on the carrier engagement surface to allow it to controllably bond to the thin glass sheet. Examples 8c and 8d show a plasma polymerized hydrocarbon surface upgrading layer formed by a hydrocarbon-containing gas (methane) and a hydrogen-containing gas (H2), and subsequently treated with a nitrogen-containing gas (ammonia). In the case of Example 8c, ammonia itself used 300 W of power, while in Example 8d, ammonia was diluted with hydrazine and polymerized at a lower power of 50 W. It was observed that the thin glass sheets and the carrier having the surface modifying layer formed according to Examples 8a-8d were not permanently adhered after annealing at 450 ° C, that is, they were able to be preserved in the portion (c) of the 400 ° C temperature test. . Degassing tests are not performed on these samples. Moreover, these examples are strong enough to be preserved in FPD processing (including the vacuum test (1), wet process test (2), and ultrasonic test (5) described above, and remain removed by application of sufficient peel force. Engage. Debonding allows removal of the device fabricated on the thin glass and reuse of the carrier.

The thin glass sheet bonded to each of the carriers according to the example of Table 8 is a substrate made of Corning® Willow® glass, which is an aluminoborosilicate-free alkali metal glass (available from Corning Incorporated, Corning). NY) and has a thickness of 100, 130 and 150 microns. Use oxygen plasma before bonding Next, SC1 and/or SC2 chemistry and standard cleaning techniques are used to clean Willow® glass.

In the example of Table 8, although the joint surface on which the surface modifying layer is disposed is glass, it is not necessary to be in this case. Alternatively, the bonding surface can be another suitable material having surface energy and properties similar to glass, such as germanium, polycrystalline germanium, single crystal germanium, ceramic, glass-ceramic, sapphire or quartz.

Polar groups are introduced into the carbonaceous surface modifying layer by N2 treatment

Another example of using a plasma polymeric film to adjust the surface energy of a bonding surface and creating a surrogate polar bonding site on the bonding surface is a surface modifying layer film from a carbon source (eg, a carbon containing gas, such as methane) and from hydrogen. The deposition of H2 followed by the nitrogen treatment of the just-formed surface modifying layer. Nitrogen treatment to form a nitrogen-based polar group on the surface modifying layer can be performed by plasma treatment using N2 gas. Deposition of the surface modifying layer can occur at atmospheric or reduced pressure and is performed using plasma excitation, such as DC or RF parallel plates, inductively coupled plasma (ICP), electron cyclotron resonance (ECR), downstream Microwave or RF plasma. The plasma polymerized surface modifying layer can be disposed on a carrier, a sheet, or both. As indicated above in connection with the examples of Table 3, plasma polymerization produces a layer of highly crosslinked material. Control of the reaction conditions and source gases can be used to control the thickness, density, and chemistry of the surface modifying layer to tailor the functional groups for the desired application, and by controlling the properties of the film, the surface energy of the bonding surface can be adjusted. The nitrogen-based polar groups formed during the subsequent plasma treatment are not condensed with the sterol groups to cause permanent covalent bonding, and thus can be controlled during subsequent processing to place the film or structure on the sheet. The degree of engagement between the carriers.

In the examples of Table 9 below, various conditions were used for nitrogen treatment of the plasma polymeric membrane deposited on a glass carrier. The glass carrier is a substrate made of Corning® Eagle XG® aluminoborosilicate free alkali metal display glass (available from Corning Incorporated, Corning NY). The vehicle is cleaned using SC1 and/or SC2 chemistry and standard cleaning techniques prior to deposition of the surface modifying layer. A surface modification layer was deposited in an Inductively Coupled Plasma (ICP) configuration mode using an Oxford Plasmalab 380 ICP (available from Oxford Instruments, Oxfordshire UK) with the carrier placed on a platform to apply 50 W of 13.56 MHz RF energy. On the platform, a coil is placed over the platform, and 1500 W of 13.5 MHz RF energy is applied to the coil. 20 sccm of methane (CH4) and 40 sccm of hydrogen (H2) were flowed into the chamber at a pressure of 5 mTorr. The surface treatment time was 60 sec, and for all of the samples listed in Table 9, the platform temperature was 30C. After the previous deposition, the surface modifying layer was treated with nitrogen. Specifically, during processing, the 13.56 MHz RF energy of the specified wattage (indicated in the "RF Bias" column) is applied to the platform, with coils placed above the platform, specifying the wattage (in the "Coil" column The 13.5 MHz RF energy is applied to the coil. N2 flows into the chamber at a rate of 40 sccm for the time listed in the time table (measured in seconds-s). Thus, for example, the notation for the nitrogen treatment of Example 9a in Table 9 is interpreted as follows: In an Oxford ICP apparatus, 40 sccm of N2 is flowed into a chamber having a pressure of 5 mTorr; and 1500 W of 13.5 MHz RF energy is applied to the sprinkler. And 300W of 13.56MHz RF energy is applied to the platform on which the carrier is placed, the platform temperature is controlled to 30C; and the process is performed for 10 seconds. The notation of the remaining instances can be interpreted in a similar manner. Surface energy is obtained by using three different test liquids (deionized water in this case (shown in column "W"), ten The contact angle (CA) and the Wu model of hexadecane (shown in column "HD") and diiodomethane (shown in column "DIM") are calculated in mJ/m2 (millijoules per square meter). For surface energy, the polar component (P) and the dispersed component (D), as well as the total energy (T), are shown.

Examples 9a-9j show various conditions for nitrogen treatment of a surface modification layer of methane/hydrogen formation, whereby various surface energies can be obtained, i.e., from about 53 mJ/m ² (Example 9i) to about 63 mJ/m ² (example) The surface energy of 9b), which is suitable for bonding to a thin glass sheet. These surface energies obtained after the nitrogen treatment are increased from about 42 mJ/m ² (obtained from the base layer formed from the methane-hydrogen plasma polymerization). It was observed that the thin glass sheets and the carrier having the surface modifying layer formed according to Examples 9a-9j were not permanently adhered after annealing at 450 ° C, that is, they successfully completed part (c) of the 400 ° C temperature test. Degassing tests are not performed on these samples. Moreover, these examples are strong enough to be preserved in FPD processing (including the vacuum test (1), wet process test (2), and ultrasonic test (5) described above, and remain removed by application of sufficient peel force. Engage. Debonding allows removal of the device fabricated on the thin glass and reuse of the carrier.

The thin glass sheet bonded to each of the carriers according to the example of Table 9 is a substrate made of Corning® Willow® glass, which is an aluminoborosilicate-free alkali metal glass (available from Corning Incorporated, Corning). NY) and has a thickness of 100, 130 and 150 microns. Prior to bonding, the Willow® glass is cleaned using oxygen plasma followed by SC1 and/or SC2 chemistry and standard cleaning techniques.

In the example of Table 9, although the joint surface on which the surface modifying layer is disposed is glass, it is not necessary to be in this case. Alternatively, the bonding surface can be another suitable material having surface energy and properties similar to glass, such as germanium, polycrystalline germanium, single crystal germanium, ceramic, glass-ceramic, sapphire or quartz.

Polar groups are introduced into the carbonaceous surface modifying layer by sequential N2 followed by H2 treatment

Another example of using a plasma polymer film to adjust the surface energy of the bonding surface and creating alternative polar bonding sites on the bonding surface is a surface modifying layer film from a carbon source (eg, methane (carbon containing gas)) and from hydrogen. The deposition of H2 followed by the sequential formation of the surface modifying layer of nitrogen followed by hydrogen treatment. Deposition of the surface modifying layer can occur at atmospheric or reduced pressure and is performed using plasma excitation, such as DC or RF parallel plates, inductively coupled plasma (ICP), electron cyclotron resonance (ECR), downstream Microwave or RF plasma. The plasma polymerized surface modifying layer can be disposed on a carrier, a sheet, or both. As indicated above in connection with the examples of Table 3, plasma polymerization produces a layer of highly crosslinked material. Control of the reaction conditions and source gases can be used to control the thickness, density, and chemistry of the surface modifying layer to tailor the functional groups for the desired application, and by controlling the properties of the film, the surface energy of the bonding surface can be adjusted. Nitrogen-based polarity formed during subsequent plasma processing The group does not condense with the sterol group to cause permanent covalent bonding, and thus the degree of bonding between the sheet and the carrier can be controlled during subsequent processing to effect placement of the film or structure on the sheet.

In the examples of Table 10 below, various conditions were used to treat the plasma polymeric film deposited on the glass carrier (using nitrogen and subsequently sequentially utilizing hydrogen). The glass carrier is a substrate made of Corning® Eagle XG® aluminoborosilicate free alkali metal display glass (available from Corning Incorporated, Corning NY). The vehicle is cleaned using SC1 and/or SC2 chemistry and standard cleaning techniques prior to film deposition. Films were deposited in an Inductively Coupled Plasma (ICP) configuration mode in an Oxford Plasmalab 380 ICP (available from Oxford Instruments, Oxfordshire UK) with the carrier placed on a platform to apply 50 W of 13.56 MHz RF energy to the platform. A coil is placed above the platform to apply 1500 W of 13.5 MHz RF energy to the coil. 20 sccm of methane (CH4) and 40 sccm of hydrogen (H2) were flowed into the chamber at a pressure of 5 mTorr. The surface treatment time was 60 sec, and for all of the samples listed in Table 9, the platform temperature was 30C. After the previous deposition, the surface modifying layer was sequentially treated with nitrogen and then treated with hydrogen. Specifically, in each case, for nitrogen treatment: 40 cm of N2 was flowed into the chamber, and 1500 W of 13.5 MHz RF energy was applied to the chamber; the chamber was at a pressure of 5 mTorr; 13.56 MHz RF energy is applied to the platform; and processing is performed for 60 seconds. Subsequently, during the hydrogen treatment, the 13.56 MHz RF energy of the specified wattage (indicated in the "RF" column of Table 10) is applied to the platform, with a coil placed above the platform, which will specify the wattage (in the "Coil" column It is pointed out that the 13.5 MHz RF energy is applied to the coil. H2 flows into the chamber at a rate of 40 sccm for the time listed in the chronograph (in seconds) -s). Thus, for example, the notation for the hydrogen treatment of Example 10a (after film deposition and its N2 treatment as described above) in Table 10 is interpreted as follows: In an Oxford ICP apparatus, 40 sccm of H2 is flowed into a chamber having a pressure of 20 mTorr. In the chamber; 750 W of 13.5 MHz RF energy was applied to the showerhead; and 50 W of 13.56 MHz RF energy was applied to the platform on which the carrier was placed; and the process was performed for 15 seconds. The notation of the remaining instances can be interpreted in a similar manner. The surface energy is obtained by using three different test liquids (in this case, deionized water (shown in column "W"), hexadecane (shown in column "H"), and diiodomethane (column "DIM"). The contact angle (CA) and the Wu model shown in )) are calculated in mJ/m2 (millijoules per square meter). For surface energy, the polar component (P) and the dispersed component (D), as well as the total energy (T), are shown.

The sequence of the plasma-polymerized surface modifying layer formed by methane-hydrogen N2 and subsequent H2 plasma treatment can be carried out under various conditions to achieve various surface energies. As seen from Table 10, the surface energy was varied from about 60 mJ/m ² (Example 10d) to about 64 mJ/m ² (Examples 10a, 10n, 10o, and 10p), which were suitable for bonding to thin glass sheets. It was observed that the thin glass sheets and the carrier having the surface modifying layer formed according to Examples 10a-10p were not permanently adhered after annealing at 450 ° C, that is, they were able to successfully complete part (c) of the 400 ° C treatment test. Moreover, these examples are strong enough to be preserved in FPD processing (including the vacuum test (1), wet process test (2), and ultrasonic test (5) described above, and remain removed by application of sufficient peel force. Engage. Debonding allows removal of the device fabricated on the thin glass and reuse of the carrier.

The thin glass sheet bonded to each of the carriers according to the example of Table 10 is a substrate made of Corning® Willow® glass, which is an aluminoborosilicate-free alkali metal glass (available from Corning Incorporated, Corning). NY) and has a thickness of 100, 130 and 150 microns. Prior to bonding, the Willow® glass is cleaned using oxygen plasma followed by SC1 and/or SC2 chemistry and standard cleaning techniques.

In the example of Table 10, although the joint surface on which the surface modifying layer is disposed is glass, it is not necessary to be in this case. Alternatively, the bonding surface can be another suitable material having surface energy and properties similar to glass, such as germanium, polycrystalline germanium, single crystal germanium, ceramic, glass-ceramic, sapphire or quartz.

As a variation of the examples in Table 10, the sequential nitrogen reforming of the methane-forming surface is also performed followed by hydrogen treatment. In this case, when an initial surface modifying layer is formed by plasma polymerization on a glass carrier, methane (without hydrogen) is used alone. Specifically, 40 sccm of methane was allowed to flow at 1500/50 W for 60 seconds under a pressure of 5 mTorr. The surface energy measurement was about 42 mJ/m ² . After sequential processing with nitrogen (40 sccm N2, at a pressure of 5 mTorr, 1500/50 W power for 15 seconds) and then hydrogen (40 sccm H2, at a pressure of 5 mTorr, 1500/50 W power for 15 seconds), the carrier was bonded The surface energy achieved on the surface is increased to about 64 mJ/m ² , which is suitable for joining thin glass sheets to glass carriers.

The order of N2 and H2 treatment of the carbonaceous surface modifying layer as described above achieves a surface energy of about 64 mJ/m2 and forms an initial room temperature bond with the thin glass sheet, wherein the joint front end speed is slightly smaller than that of the fluorinated surface modification layer. Typical situation. As in the examples in Table 10, it was observed that these samples did not permanently adhere after annealing at 450 ° C, that is, they were able to successfully complete part (c) of the 400 ° C treatment test. Moreover, these examples are strong enough to be preserved in FPD processing (including the vacuum test (1), wet process test (2), and ultrasonic test (5) described above, and remain removed by application of sufficient peel force. Engage. Debonding allows removal of the device fabricated on the thin glass and reuse of the carrier.

Polar groups are introduced into the carbonaceous surface modifying layer by sequential N2-O2 followed by N2 treatment

Based on an attempt to create more polar quinone imine groups on the surface to increase the speed of the joint front end, the order of the carbonaceous surface modifying layer was explored N2-O2 followed by N2 plasma treatment.

An example of using a plasma polymer film to adjust the surface energy of the bonding surface and creating a substitute polar bonding site on the bonding surface is a carbonaceous surface modifying layer film from a carbon source (eg, a carbonaceous gas (eg, methane)) and The deposition from hydrogen H2, followed by the sequence of the surface modifying layer just formed, N2-O2 and subsequent N2 treatment. Deposition of the surface modifying layer can occur at atmospheric or reduced pressure and is performed using plasma excitation, such as DC or RF parallel plates, inductively coupled plasma (ICP), electron cyclotron resonance (ECR), downstream Microwave or RF plasma. Plasma The polymeric surface modifying layer can be disposed on a carrier, a sheet, or both. As indicated above in connection with the examples of Table 3, plasma polymerization produces a layer of highly crosslinked material. Control of the reaction conditions and source gases can be used to control the thickness, density, and chemistry of the surface modifying layer to tailor the functional groups for the desired application, and by controlling the properties of the film, the surface energy of the bonding surface can be adjusted. The nitrogen-based polar groups formed during the subsequent plasma treatment are not condensed with the sterol groups to cause permanent covalent bonding, and thus can be controlled during subsequent processing to place the film or structure on the sheet. The degree of engagement between the carriers.

In the examples of Table 11 below, various conditions were used to treat the plasma polymeric film deposited on the glass carrier to increase surface energy and incorporate polar groups. The glass carrier is a substrate made of Corning® Eagle XG® aluminoborosilicate free alkali metal display glass (available from Corning Incorporated, Corning NY). The vehicle is cleaned using SC1 and/or SC2 chemistry and standard cleaning techniques prior to deposition of the surface modifying layer.

In step 1, a surface modification layer is deposited in an Inductively Coupled Plasma (ICP) configuration mode in an Oxford Plasmalab 380 ICP (available from Oxford Instruments, Oxfordshire UK), where the carrier is placed on a platform, 50 W 13.56 MHz RF energy is applied to the platform with a coil placed over the platform to apply 1500 W of 13.5 MHz RF energy to the coil. 20 sccm of methane (CH4) and 40 sccm of hydrogen (H2) were flowed into the chamber at a pressure of 5 mTorr. The surface treatment time was 60 sec, and for all of the samples listed in Table 11, the platform temperature was 30C.

After the previous deposition in step 1, in step 2, the surface modifying layer is treated with nitrogen and oxygen. To be precise, during the processing of step 2, 50W will be 13.56 MHz RF energy is applied to the platform with a coil placed over the platform to apply 800 W of 13.5 MHz RF energy to the coil. N2 and O2 flow into the chamber at the specified rate (in sccm) for the time listed in the timesheet (measured in seconds-s). Thus, for example, the notation of step 2 of Example 11a in Table 11 is interpreted as follows: After the surface modification layer deposition in step 1, in an Oxford ICP apparatus, 35 sccm of N2 is introduced with 5 sccm of O2 into a pressure of 15 mTorr. In the chamber; 800 W of 13.5 MHz RF energy was applied to the showerhead; and 50 W of 13.56 MHz RF energy was applied to the platform on which the temperature of the carrier was placed to 30 ° C; and the treatment was carried out for 5 seconds. The notation of the remaining instances can be interpreted in a similar manner.

After the previous treatment of step 2, in step 3, the surface modifying layer is treated with nitrogen. Specifically, during the process of step 3, 50 W of 13.56 MHz RF energy is applied to the platform, with coils placed above the platform, and 1500 W of 13.5 MHz RF energy applied to the coil. N2 flows into the chamber at the specified rate (in sccm) for the time listed in the timesheet (measured in seconds-s). Thus, for example, the notation for step 3 of Example 11a in Table 11 is interpreted as follows: after the surface modifying layer deposition in step 1, and after the nitrogen-oxygen treatment in step 2, in the Oxford ICP apparatus, 40 sccm N2 flows into the chamber with a pressure of 5 mTorr; 1500 W of 13.5 MHz RF energy is applied to the shower head; and 50 W of 13.56 MHz RF energy is applied to the platform on which the temperature of the carrier is placed to 30 ° C And the process is carried out for 15 seconds. The notation of the remaining instances can be interpreted in a similar manner.

The surface energy is obtained by using three different test liquids (deionized water, hexadecane and diiodomethane in this case) and the contact angle (CA) and Wu mode. Type, calculated in mJ/m2 (millijoules per square meter). For surface energy, the total surface energy (T, which includes the polar component and the dispersed component) is shown. The joining energy was calculated as mJ/m2 as described above. The number of bubbles after the initial bonding is indicated in the column named "23 C% area", and the number of bubbles after the temperature test at 400 ° C is indicated in the column named "400 C% area". The number of bubbles is determined by an optical scanner as described below in connection with "degassing". Finally, the change in bubble area from the initial time at 23 ° C to 400 ° C after the temperature test is indicated in the column entitled "△% area".

Examples 11a-11e demonstrate that various conditions can be applied to the sequential nitrogen-oxygen of the surface modification layer of methane/hydrogen formation followed by nitrogen treatment whereby various surface energies can be obtained, i.e., from about 65 mJ/m ² (Examples 11a and 11e). ) to about 70 mJ/m ² (Examples 11b and 11d), the surface energies are suitable for bonding to thin glass sheets. These surface energies obtained after sequential nitrogen-oxygen and subsequent nitrogen treatment are increased from about 40-50 mJ/m ² (obtained from the base layer formed from methane-hydrogen plasma polymerization). It was observed that the thin glass sheets and the carrier having the surface modifying layer formed according to Examples 11a-11f were not permanently adhered after annealing at 400 ° C, that is, they successfully completed part (c) of the 400 ° C temperature test. As shown in Examples 11a-11e, the % bubble area change during annealing at 400 °C is consistent with no outgassing. On the other hand, the % bubble area change of Example 11f during annealing at 400 °C is consistent with some outgassing of the material in the surface modification layer. Therefore, step 3 is important in order to obtain no surface degassing of the surface modifying layer deposited according to the conditions in Table 11. However, under the other deposition/processing conditions used in steps 1 and 2, step 3 may not necessarily result in a degassing result similar to that obtained in step 3 of Examples 11a-e. In addition, these examples are strong enough to be preserved in FPD processing (including vacuum test (1), wet process test (2), and ultrasonic test (5), and can be maintained after 400 °C temperature test. The peeling force is applied to disengage. Debonding allows removal of the device fabricated on the thin glass and reuse of the carrier.

The effects of these sequential steps on surface energy, bonding energy and blistering are shown in Table 11. Increasing the oxygen fraction in the N2-O2 step reduces surface energy and increases foaming during the degassing test. The use of a short (about 5 seconds) low oxygen fraction (38/2) N2-O2 step followed by a short (15 seconds) N2 plasma treatment (Example 11d) yielded a surface energy of 69 mJ/m2 during a 400 °C temperature test. And 1.2% of the bubble area (% bubble area change from 23 ° C to -0.01, indicating no outgassing). The performance of samples 11a-e is equivalent to a fluorinated surface modifying layer for applications tested at temperatures up to 400 °C.

The thin glass sheet bonded to each of the carriers according to the example of Table 11 is a substrate made of Corning® Willow® glass, which is aluminoboroic acid. The salt is free of alkali metal glass (commercially available from Corning Incorporated, Corning NY) and has thicknesses of 100, 130 and 150 microns. Prior to bonding, the Willow® glass is cleaned using oxygen plasma followed by SC1 and/or SC2 chemistry and standard cleaning techniques.

In the example of Table 11, although the joint surface on which the surface modifying layer is disposed is glass, it is not necessary to be in this case. Alternatively, the bonding surface can be another suitable material having surface energy and properties similar to glass, such as germanium, polycrystalline germanium, single crystal germanium, ceramic, glass-ceramic, sapphire or quartz.

The above examples illustrate how an inductively coupled plasma (ICP) system can be utilized to deposit a thin organic surface modifying layer suitable for controllably bonding a thin glass sheet to a glass carrier for processing by a device. However, this solution is a concern for the adjustability of display applications where a large area substrate is advantageous. ICP tools utilize planar, cylindrical or hemispherical coils to induce a coupling current to create a time-varying magnetic field that causes ion circulation. Typically, the second RF source is connected to a platform on which the substrate is placed. The advantage of ICP plasma is that the ICP source can achieve high-order ionization independently of substrate bias controlled by the platform RF source. Current parallel plate reactive ion etch (RIE) systems are unable to achieve higher order ionization. In addition, the bias and ionization are coupled via RF power and pressure. TEL and others have scaled the ICP etcher to Gen 5, but scaling to the larger ones poses a challenge to producing a uniform ICP plasma source. On the other hand, the RIE mode process is suitable for parallel plate tools that have been scaled to Gen 10. Accordingly, the inventors explored ways to achieve results similar to those achieved by utilizing the ICP tools described above in the RIE mode process.

RIE mode surface modification layer from non-fluorinated source material by using only Oxford's RIE mode (no coil power) and 200 W bias power (equivalent to deposition for fluorinated surface modification layers) The initial effort resulted in a dark thick layer that could be modified by nitrogen to bond to a thin glass sheet. However, such a dark material produced a number of bubbles after undergoing a 400 ° C treatment test, which covered about 25% of the joint area. Characterization of the dark deposit by spectral ellipsometry confirmed that the film was about 100 nm thick and exhibited a more narrow optical band gap, which is 0.6 eV relative to 1.7 eV of the ICP deposition surface modifying layer. Based on this result, it is concluded that the material may be graphite and increasing the hydrogen content would be a consideration for reducing foaming.

Experiments were performed to capture optical emission spectroscopy (OES) spectra for the enantiomeric RIE process variable H2/CH4 ratio, RF power, and pressure. However, within the process window of the Oxford tool used, these ratios are not matchable. However, this experiment confirms that the process will benefit from the extremely high hydrogen dilution, high RF power, and low pressure of the polymer forming gas.

In addition to the OES that directs the process change from ICP mode to RIE mode, residual gas analysis (RGA) is used for the hydrogen/methane ratio, RF power, and pressure variation in the RIE mode present in the enantiomer Oxford. Gas phase substance. The m/e=/16 versus pressure and H2/CH4 gas ratio contour plots again confirm that a high hydrogen dilution is beneficial for matching the ICP ratio of about 44. Higher alkanes are associated with a reduced H2/CH4 gas ratio and increased pressure. The contour plot shows that m/e = 28/16 increases with both RF and H2/CH4 gases. Fitting the RGA response surface suggests that the H2/CH4 and C2H6/CH4 ratios can be matched at 40:1 H2/CH4, 25mTorr 275W RF. Carbonaceous RIE mode deposited using this condition The surface modification layer matches the thickness of about 6 nm of the ICP mode carbonaceous surface modifying layer and the 1.6 eV optical band gap. Initial experiments with nitrogen plasma treatment of a carbonaceous RIE surface modifying layer also confirmed low foaming.

The kinetics of the deposition of the RIE mode carbonaceous surface modifying layer using the process identified by the RGA experiment are shown in Figures 14 and 15. The surface energy including the total surface energy (T) and the polar component (P) and the dispersion component (D) is shown in Fig. 14. As shown in Fig. 14, the surface energy is relatively unchanged, with a slight peak at 60 sec deposition time, and in Fig. 15 it is seen that the film thickness increases almost linearly on a double logarithmic scale. This is not a self-limiting process because the etch-back from hydrogen cannot keep up with polymer deposition.

As discussed above, it is understood from experience that: About 50mJ/m2 or A surface energy of 65 mJ/m2 is beneficial to minimize bubble area during initial room temperature bonding and during thermal cycling. According to Figure 14, it can be seen that the surface energy is just on the boundary line. In some cases, this may be suitable for joining the sheet to the carrier, depending on the time-temperature cycle that will be experienced, and on other FPD processes that must be experienced. On the other hand, however, it would be beneficial to increase the surface energy of this surface modifying layer. Any of the above-described subsequent treatments may be used, for example, ammonia treatment, nitrogen treatment, sequential nitrogen followed by hydrogen treatment, nitrogen-oxygen treatment, sequential nitrogen-oxygen followed by nitrogen treatment. For example, nitrogen-oxygen treatment will be described in conjunction with Table 12.

Polar groups are introduced into the carbonaceous surface modifying layer by nitrogen-oxygen treatment

Another example of using a plasma polymeric film to adjust the surface energy of the bonding surface and creating a surrogate polar bonding site on the bonding surface is a thin surface modifying layer film in a RIE mode from a carbon source (eg, methane, ie, carbon containing gas) And deposition from hydrogen (H2) followed by nitrogen-oxygen treatment of the just-formed surface modifying layer. Usable example Nitrogen-oxygen treatment is performed as a nitrogen-oxygen plasma treatment. The deposition of the surface modifying layer can occur at atmospheric pressure or reduced pressure. The plasma polymerized surface modifying layer can be disposed on a carrier, a sheet, or both. As indicated above in connection with the examples of Table 3, plasma polymerization produces a layer of highly crosslinked material. Control of the reaction conditions and source gases can be used to control film thickness, density, and chemistry to tailor the functional groups to be used, and by controlling the properties of the film, the surface energy of the bonding surface can be adjusted. The nitrogen-based polar group formed during the subsequent nitrogen-oxygen treatment does not condense with the sterol group to cause permanent covalent bonding, and thus can be controlled during subsequent processing to place the film or structure on the sheet. The degree of engagement with the carrier.

In the examples of Table 12 below, various conditions were used to deposit a plasma polymerized surface modifying layer film onto a glass carrier. The glass carrier is a substrate made of Corning® Eagle XG® aluminoborosilicate free alkali metal display glass (available from Corning Incorporated, Corning NY). The vehicle is cleaned using SC1 and/or SC2 chemistry and standard cleaning techniques prior to film deposition. A surface modification layer was deposited in an RIE configuration mode in an Oxford Plasmalab 380 ICP (available from Oxford Instruments, Oxfordshire UK), where the carrier was placed on a platform and 275 W of RF energy was applied to the platform, placed above the platform. There is a coil that does not apply energy to the coil. In step 1, 2 sccm of methane (CH4) and 38 sccm of hydrogen (H2) were flowed into a chamber at a pressure of 25 mTorr. The surface treatment time was 60 sec, and for all of the samples listed in Table 12, the platform temperature was 30C. After the previous deposition, the surface modifying layer is treated with nitrogen and oxygen in step 2. Specifically, during the processing of step 2, the 13.56 MHz RF energy of the specified wattage (indicated in the "RF" column) is applied to the platform, with a coil placed over the platform, no energy applied to the coil. N2 The rate of sccm listed in the column "N2" flows into the chamber, and O2 flows into the chamber at the rate of sccm listed in the "O2" column for the time listed in the "Time (s)" column of the table. (counted as seconds - s). The chamber is at the pressure (in mTorr) listed in the "Pr" column. Thus, for example, the notation for the nitrogen and oxygen treatment of step 2 of Example 12b in Table 12 is as follows: In an Oxford ICP apparatus, 25 sccm of N2 is passed together with 25 sccm of O2 into a chamber having a pressure of 10 mTorr; 13.5 MHz RF energy was applied to the platform on which the carrier was placed, the platform temperature was controlled to 30 C; and the process was performed for 10 seconds. The notation of the remaining instances can be interpreted in a similar manner.

The surface energy is obtained by using three different test liquids (in this case, the contact angle of deionized water (W), hexadecane (HD) and diiodomethane (DIM)) and the Wu model, in mJ/m2 (m. Joules per square meter) to calculate. For surface energy, the polar component (P) and the dispersed component (D), as well as the total energy (T), are shown. Also shows the thickness of the surface modification layer ("th" in angstroms), the deposition of the surface modification layer and the average surface roughness of the carrier after the N2-O2 treatment ("Ra" in angstroms), bonding Energy ("BE" in mJ/m2), and the area of the bubble after initial bonding of the thin glass sheet to the carrier via the surface modifying layer at room temperature and the area of the bubble after heating the carrier via the 400 °C process test The % bubble area change ("△ bubble area").

The thin glass sheet bonded to each of the carriers according to the example of Table 12 is a substrate made of Corning® Willow® glass, which is an aluminoborosilicate-free alkali metal glass (available from Corning Incorporated, Corning). NY) and has a thickness of 100, 130 and 150 microns. Use oxygen before the joint The slurry is then cleaned with SC1 and/or SC2 chemistry and standard cleaning techniques to clean Willow® glass.

In the example of Table 12, although the joint surface on which the surface modifying layer is disposed is glass, this need not be the case. Alternatively, the bonding surface can be another suitable material having surface energy and properties similar to glass, such as germanium, polycrystalline germanium, single crystal germanium, ceramic, glass-ceramic, sapphire or quartz.

According to the treatment in the example of Table 12, it can be seen that after the treatment at 400 ° C: Examples 12a to 12j all have a bubble area change of less than 2, which is consistent with no outgassing at this temperature, see the bubble % column in Table 12; And the samples 12a, 12b, 12c, 12g, and 12j each have bonding energies that allow disengagement of the sheet from the carrier after this temperature test, see the BE column in Table 12; but examples 12d, 12e, 12f, 12h, and 12i cannot Debonded after the 400 °C process test, as indicated by the value 2500 in the BE column of Table 12.

According to the example of Table 12, surface energy, bubble area, bonding energy, and thickness were mapped by ellipsometry with % O2, RF, and pressure. It can be seen that the reduction in thickness correlates with increased RF power (compare Example 12g with Example 12b) and % O2 (compared with Example 12a with Example 12b), consistent with ashing of the hydrocarbon layer. Bonding energy is only dependent on pressure: samples treated at 10 mTorr can be debonded after annealing at 400 °C (see Examples 12a, 12b, 12c, 12g). The samples treated at 35 mTorr and above were not debonded. See, for example, Example 12d, which was processed at a pressure of 40 mTorr, having an engagement energy of 2,500, and Example 12e having a pressure of 70 mTorr and an engagement energy of 2,500. In the "BE" column, the joint energy of 2500 indicates that the thin glass piece cannot be disengaged from the carrier. The surface energy of all treated membranes is 65-72 mJ/m2. It is independent of thickness. See examples 12a through 12i and 12k. These results suggest that high pressure N2-O2 plasma treatment produces a discontinuous film. In fact, the high pressure rapidly sharpens the films, whereby lower pressures are beneficial. As for foaming, the amount seems to decrease as % O2*RF increases. In addition, it can be seen that the partial pressure of H2O increases with the increase of %O2 and the increase of RF; the thickness of the surface modified layer decreases with the increase of the pressure in step 2, and the % foaming area increases with the increase of pressure (so during step 2) Low pressure is beneficial; as the processing time increases, the thickness of the surface modifying layer decreases and the polar groups decrease, thus advantageously producing a shorter processing time.

Look for a balance between bonding energy and blistering. The starting point for the nitrogen-oxygen treatment was 50% O2, 10 mTorr 300 W and varying process times. Three sets of samples were prepared using 20 second, 60 second, and 180 second RIE CH4-H2 deposition followed by 0, 5, 15 and 60 seconds of N2-O2 plasma treatment. Surface energy and bonding energy peaked at 5-15 seconds N2-O2 plasma treatment time, independent of CH4-H2 deposition time. The thin 20-second CH4-H2 layer was ground and the thin glass piece was permanently bonded to the carrier. The peak appears before the polymer layer is ground, which is consistent with the formation of polar groups on the polymer film, rather than just the sharpening of the exposed glass substrate. The bubble area does increase with increasing deposition time of the surface modifying layer, so it is not beneficial to only increase the thickness of the surface modifying layer to avoid excessive sharpening during subsequent N2-O2 surface treatment. Therefore, a good compromise between bonding and bubble area is the balance of surface modification layer deposition time and N2-O2 processing time. Based on equilibrium surface modification layer deposition time (not too long deposition time, thus will produce greater thickness, resulting in increased outgassing) and N2-O2 processing time - not too long processing time for grinding or shifting In addition to the surface modifying layer (resulting in permanent bonding of the carrier to the sheet), but long enough to incorporate polar groups into the surface modifying layer. Good The tradeoff is a 60 second RIE deposition of the carbonaceous layer followed by a short N2-O2 treatment time of 5-10 seconds. Examples 12a, 12b, 12c, 12g, and 12k are applicable to the RIE mode.

Incorporating polar groups on the surface modifying layer

XPS N1s material formation was used to study the mechanism by which N2-O2 plasma treatment produces highly polar surfaces. In order to study and confirm the formation of substances in these surface modification layers, the surface chemistry of the relatively thick film of CH4/H2 deposited on EagleXG® glass wafers was investigated to achieve complete coverage of the glass by the thick films, and subsequently Different durations were treated with N2/O2 plasma. The advantage of a thick hydrocarbon membrane is that it allows us to distinguish between these nitrogen species present only on the hydrocarbon membrane and to separate these nitrogen species from their nitrogen species present on the exposed glass.

The surface composition of the EagleXG® glass wafer was first exposed to 600 seconds of CH4/H2 plasma to deposit a thick hydrocarbon film, followed by exposure to N2/O2 plasma for 5, 15, 60 and 600 seconds. For the 5 second and 15 second treatments, no elements (such as Al and Ca) present in the glass were detected, indicating that in these cases, the carbonaceous film layer is thicker than the probe depth of the XPS. The needle depth is about 10 nm.

Exposing the carbonaceous film to the N2/O2 plasma for 60 seconds and 600 seconds produces a certain degree of thinning of the carbonaceous layer because, under these conditions, the XPS can detect the elements present in the glass. This observation is additionally confirmed by considering the surface concentration of carbon. For 60 seconds and 600 seconds of treatment, the C concentration is less than 10 at%, which strongly implies that for these conditions, the surface is partially covered by the carbonaceous layer.

The NH3+ species is detected only when the substantial mass of the carbonaceous membrane has been etched away. This strongly suggests that NH3+ substances may only be present on the glass, and other substances are involved in the main reaction between the nitrogen and the carbonaceous layer. All on the surface The formation of the substance of the nitrogen species as a percentage of the atom (i.e., the fraction of nitrogen detected by the fraction x of the substance) is presented in Table 13 below.

It can be seen that the main effect of this N2-O2 treatment is the etching of the carbonaceous surface modifying layer. In fact, very little carbonaceous material is present on the surface for 60 seconds and 600 seconds of processing. Other observations are that nitrogen species are present on the surface modifying layer even after very short N2-O2 treatment times (eg, 5 seconds and 15 seconds). Thereafter, the nitrogen species rapidly decreases, while the ammonia species (indicating the presence of the underlying glass surface) rapidly increases. The XPS evaluation of the carbonaceous material formation of the 5 second N2-O2 plasma treatment of the carbonaceous surface modifying layer also revealed that several different substances containing oxygen and nitrogen were present on the surface modifying layer. The presence of oxygenates results in the recognition that a separate O2 plasma may be sufficient to impart a polar group to the surface modifying layer. Indeed, the situation found is exactly the same, and it is discussed below.

Based on the assumption that the NH3 ⁺ species is present only on the glass and not on the carbonaceous layer, the surface coverage can be estimated by calculating the ratio of NH3 ⁺ /Σ (all nitrogen compounds). The results of this surface coverage estimate are given in Figure 17. There is a small change between 5 seconds and 15 seconds. The largest change occurred between 15 seconds and 60 seconds of the N2-O2 plasma treatment time.

The model of N2-O2 plasma treatment of the carbonaceous surface modification layer is as follows. The deposition of CH4-H2 produces a continuous hydrocarbon layer. In the first second of the N2-O2 plasma treatment, the polar-NH2 group is formed on the surface of the polymer as the hydrocarbon layer is oxidized and ground.醯 The imido group or the guanamine group can also be formed at this time, but XPS is inconclusive. In the case of longer N2-O2 plasma treatment, polymer removal reaches the glass surface where the polar-NH3+ group is formed by the interaction between the N2-O2 plasma and the glass surface.

O2 alone as surface treatment of surface modification layer

As an alternative to the N2-O2 treatment of the carbonaceous layer, it is also explored to use O2 alone to increase surface energy and create polar groups on the carbonaceous layer. As indicated above, the formation of the XPS carbon material by the 5 second N2-O2 plasma treatment of the carbonaceous layer confirmed that the oxygen-containing material did exist on the surface modification layer. Therefore, an O2 treatment of the carbonaceous layer is attempted. O2 processing is performed in both the ICP mode and the RIE mode.

In the ICP mode, the base carbonaceous layer was formed according to step 1 in Table 11 above. The surface treatment of step 2 is then carried out by flowing 40 sccm O2, 0 sccm N2, using 800/50 W power at a pressure of 15 mTorr, thereby producing a desired increase in surface energy and producing the desired polar groups on the surface of the carbonaceous layer. The thin glass sheet is easily bonded to the surface modifying layer at room temperature. Further, it was observed that the sample did not permanently adhere after annealing at 450 ° C, that is, the portion (c) of the 400 ° C treatment test was successfully completed. In addition, the sample is strong enough to be preserved in the FPD process (including the vacuum test (1), wet process test (2), and ultrasonic test (5) described above, and remains disengageable by application of sufficient peel force. . Debonding allows removal of the device fabricated on the thin glass and reuse of the carrier.

In the RIE mode, a base carbonaceous layer was formed according to step 1 in Table 12 above. The surface treatment of step 2 was then carried out by flowing 50 sccm O2, 0 sccm N2, using a power of 200 W at a pressure of 50 mTorr. Similar to the ICP mode, these conditions also produce an increase in surface energy and are in the carbonaceous layer. The desired polar group is produced on the surface. The thin glass sheet is easily bonded to the surface modifying layer at room temperature. Further, it was observed that the sample did not permanently adhere after annealing at 450 ° C, that is, the portion (c) of the 400 ° C treatment test was successfully completed. In addition, the sample is strong enough to be preserved in the FPD process (including the vacuum test (1), wet process test (2), and ultrasonic test (5) described above, and remains disengageable by application of sufficient peel force. . Debonding allows removal of the device fabricated on the thin glass and reuse of the carrier.

Thus, it can be seen that the O2 process operates in a similar manner to the N2-O2 process. Similar considerations apply to the balance between the initial surface modification layer deposition time (which increases the thickness) and the O2 treatment time.

Small amount of fluorine

A few atomic % of F, i.e., about 2.2% F, was found in the XPS analysis of the ICP mode hydrocarbon polymer deposited carbonaceous layer. This is due to the fact that Oxford is used for fluorine and chlorine etching of glass, dielectrics and metals. It has been found that a small amount of fluorine is beneficial to the nature of the modified layer of the hydrocarbon deposition surface. The typical reactor cleaning process is SF6-O2 cleaning followed by O2 cleaning and H2 plasma cleaning. Each step is 30 minutes long and includes a pumping/rinsing step between steps. SF6-O2 is used for initial cleaning because the etch rate of hydrocarbon polymers is quite higher than O2 alone. The H2 plasma cleaning step should remove most of the undefined fluorine from the deposit on the reactor wall. If H2 plasma cleaning is skipped, it will be expected that a higher amount of fluorine will be incorporated into the hydrocarbon surface modifying layer. Figure 16 skips the effect of the H2 plasma step in the case of a hydrocarbon surface modifying layer. The joint energy is reduced, causing the permanent joint to displace up to 600 ° C without a large increase in foaming. Thus, a small amount of fluorine in the hydrocarbon surface modifying layer, i.e., at least up to about 3% fluorine is beneficial.

Surface roughness

The surface roughness of the glass joint surface was examined for changes in the deposition of the surface reforming layer formed by the hydrocarbon. Specifically, a surface modification layer formed of methane-hydrogen is selected, which is subsequently sequentially treated with nitrogen and then hydrogen. Two carriers were prepared using a surface modification layer formed of methane-hydrogen, followed by sequential in situ N2 and subsequent H2 plasma treatment (20CH4 40H2 5mT 1500/50W for 60 seconds, followed by 40N2 5mT 1500/50W for 15 seconds, followed by 40H2 15mT 1500/50W 15 lasts a few seconds). The surface modifying layer of the first carrier (Example 14a) was removed by O2 plasma cleaning followed by SC1 cleaning. The surface modification of the second carrier (Example 14b) was maintained in place. The third carrier (Example 14c) was used as a reference and did not have a surface modifying layer applied thereto. AFM was used to evaluate the surface roughness of a carrier that applied a surface modifying layer and subsequently stripped it (Example 14a), a carrier that still had a surface modifying layer (Example 14b), and a reference carrier (Example 14c). The Rq, Ra, and Rz ranges measured by AFM are shown in Table 14 in nm (nano). The roughness of Examples 14a and 14b was not distinguishable from the roughness of Example 14c. It should be noted that for Example 14c, the excess z-range of the 5x5 micron scan is due to the particles in the scanned area. Thus, it can be seen that the surface modifying layer formed by the hydrocarbons of the present disclosure does not alter the surface roughness of the glass bonding surface. In some cases, the unaltered surface roughness of the joint surface can facilitate, for example, repeated use of the carrier. The glass carriers in these examples were substrates made of Corning® Eagle XG® aluminoborosilicate free alkali metal display glass (available from Corning Incorporated, Corning NY).

Overall consideration

The above separation of the sheet from the carrier was carried out in Examples 2-12 without any additional thermal or chemical energy to modify the joint interface between the sheet and the carrier at room temperature. The only energy input is mechanical tension and/or peel force.

Since the surface modifying layers of Examples 3 and 5-12 are thin organic layers, they are sensitive to oxygen in thermal and plasma processing. Therefore, these surface modifying layers should be protected during the fabrication of the device. The surface modifying layer can be protected by using a non-oxygenated environment (eg, an N2 environment) during heat treatment. Alternatively, depositing a protective coating (e.g., a thin metal layer) on the edge of the interface between the bonded thin glass sheet and the carrier is sufficient to protect the surface modifying layer from the effects of an oxygen environment at elevated temperatures.

When both the sheet and the carrier include a glass bonding surface, the surface modifying materials described in the above Examples 3 to 12 can be applied to the carrier, applied to the sheet, or applied to the surface of the carrier and the surface of the sheet to be joined together. Both. Alternatively, when one of the bonding surfaces is a polymeric bonding surface and the other bonding surface is a glass bonding surface (as further described below), the appropriate surface modifying materials described above in Examples 3 through 12 (based on the polymer) The surface energy of the bonding surface is applied to the glass bonding surface. Additionally, the entire carrier or sheet need not be made of the same material, but may include different layers and/or materials therein as long as the joining surface is adapted to receive the surface modifying layer of interest. For example, the joining surface can be glass, glass-ceramic, ceramic, tantalum or metal, wherein the remainder of the carrier and/or sheet can have different materials. For example, the sheet 20 engaging surface can have any Suitable materials include, for example, tantalum, polycrystalline germanium, single crystal germanium, sapphire, quartz, glass, ceramic or glass-ceramic. For example, the carrier 10 bonding surface can be a glass substrate, or another suitable material having surface energy similar to glass, such as germanium, polycrystalline germanium, single crystal germanium, ceramic, glass-ceramic, sapphire, or quartz.

As can be seen from the examples discussed herein, the surface modifying layer, along with its subsequent processing, provides a means to broadly alter the surface energy on the glass bonding surface. For example, it can be seen from all examples that the surface energy of the glass joint surface can vary from about 36 mJ/m2 (as in Example 5g) to about 80 mJ/m2 (Example 5f). In the case of using a non-fluorinated source material in a single-step process without subsequent surface treatment, it can be seen that the surface energy of the glass joint surface can be varied from about 37 mJ/m2 (Example 16b) to about 67 mJ/m2 (Examples 7h and 7j). . With a carbonaceous surface modifying layer and subsequent processing to increase the polar groups, it can be seen that the surface energy of the glass bonding surface can vary from about 52 mJ/m2 (Example 12j) to about 74 mJ/m2 (Example 8a). In the case of a non-fluorinated source material used in a single step process or a two step process, it can be seen that the surface energy of the glass joint surface can vary from about 37 mJ/m2 (Example 16b) to about 74 mJ/m2 (Example 8a). In the case where a fluorine-containing source material or a non-fluorine-containing source material is used to deposit the surface modifying layer and its subsequent treatment is utilized, it can be seen that the surface energy of the glass bonding surface can be changed from about 41 mJ/m 2 (Example 5 m) to about 80 mJ/m 2 ( Example 5f).

Additionally, as can be seen from the examples discussed herein, the thickness of the surface modifying layer can vary greatly. Desirable results were obtained with surface modifying layer thicknesses ranging from about 2 nm (as in Example 3) to about 8.8 nm (as in Example 12c).

Use of controlled joints

Reusable vehicle

One use of controlled bonding via a surface modifying layer (including heat treatment of materials and associated bonding surfaces) is to provide re-use of the carrier in the article, which is subject to need A process at a temperature of 600 ° C, as in the case of, for example, an LTPS process. As exemplified by Examples 2e, 3a, 3b, 4c, 4d, and 4e and the examples in Table 5 above, the surface modifying layer (including material and bonding surface heat treatment) can be used to provide repeatability of the carrier under such temperature conditions. use. Specifically, the surface modifying layer can be used to modify the surface energy of the overlapping area between the bonding area of the modified sheet (having the glass bonding surface) and the bonding area of the carrier (having the glass bonding surface), whereby the entire sheet can be After treatment, it is separated from the vehicle. The sheets may all be separated at once, or may be separated in portions, such as, for example, when the device produced on portions of the sheet is first removed, and then the remaining portion is removed to clean the carrier for reuse. In the case where the entire sheet is removed from the carrier, the carrier can be reused as it is by simply placing another sheet thereon. Alternatively, the carrier can be cleaned and loaded again by reforming the surface modifying layer to carry the sheet. Because the surface modifying layer prevents the sheet from permanently engaging the carrier, it can be used in the temperature 600 ° C process. Of course, although these surface modifying layers can be The bonding surface energy is controlled during processing at a temperature of 600 ° C, but the surface modifying layers can also be used to create a sheet and carrier combination that is resistant to processing at lower temperatures and can be used in such lower temperature applications. Control the joint. In addition, where the heat treatment of the article will not exceed 400 ° C, such as by the examples of Examples 2c, 2d, 4b, Tables 7-11 (including the examples discussed in the alternatives to the examples of Table 10), Example 12a, The surface modifying layers can also be used in the same manner as exemplified by examples of 12b, 12c, 12g, 12g and surface treatment with separate O2.

One advantage of using the surface modifying layers described herein is that the carriers can be reused in the same size, such as the surface modifying layers of the following: Examples of Table 3, Examples 4b, 4c Examples of 4d, 4e, 5 and 7-11, examples 12a, 12b, 12c, 12g, 12j and examples of surface treatment with separate O2. That is, the sheet can be removed from the carrier, and the surface modifying layer can be removed from the carrier by a non-destructive means (eg, O2 or other plasma cleaning) and reused without having to cut the carrier in any way (eg, , cut at the edge of the carrier).

Used to provide controlled joint areas

A second use of controlled bonding via a surface modifying layer (including heat treatment of the material and associated bonding surfaces) is to provide a controlled joint area between the glass carrier and the glass sheet. More specifically, where a surface modifying layer is used, a controlled joint region can be formed in which sufficient separation force separates the sheet portion from the carrier without the pair of sheets or carriers caused by the bonding Destruction, but still maintaining sufficient bonding force throughout the process to hold the sheet relative to the carrier. Referring to FIG. 6, the glass sheet 20 can be joined to the glass carrier 10 by the joint region 40. In the joint region 40, the carrier 10 and the sheet 20 are covalently bonded to each other so that they serve as a single piece. Additionally, there is a controlled joint region 50 having a perimeter 52 in which the carrier 10 and the sheet 20 are joined, but may be separated from one another, even after high temperature processing, such as in This is done after treatment at a temperature of 600 °C. Although ten controlled joint regions 50 are shown in Figure 6, any suitable number, including one, may be provided. As by the examples 2a, 2e, 3a, 3b, 4c, 4d and 4e, the above table

As exemplified by the example of 5, the surface modifying layer 30 comprising the material and the bonded surface heat treatment can be used to provide a controlled joint region 50 between the carrier 10 having a glass bonded surface and the sheet 20 having a glass bonded surface. Specifically, such surface modifying layers can be formed in the periphery 52 of the controlled bonding region 50 on the carrier 10 or on the sheet 20. Thus, when the article 2 is treated at a high temperature to form a covalent bond in the joint region 40 or processed during processing of the device, it can be provided between the carrier 10 and the sheet 20 in the region bounded by the perimeter 52. Control the bonding whereby the separation force can separate in this region (without catastrophic failure of the sheet or carrier) sheets and carriers, and the sheets and carriers will not delaminate during processing including ultrasonic processing. The controlled engagement of the present application, as provided by the surface modifying layer and any associated heat treatment, can thus improve the concept of the carrier in US '727. Specifically, although the US'727 vehicle demonstrates that the joint perimeter and non-joining center areas of the carriers are preserved during FPD processing, the FPD processing includes High temperature processing at about 600 ° C, but ultrasonic processes such as wet cleaning and resist stripping are still challenging. Specifically, it is noted that the pressure wave in this solution induces resonance in the non-bonded regions of thin glass (such as the non-joining described in US '727) because the thin glass and the carrier have little or no adhesion in the region. Force joint. Standing waves can be formed in the thin glass, wherein if the ultrasonic agitation has sufficient strength, the waves can cause vibrations, which can cause damage of the thin glass at the interface between the bonded region and the non-bonded region. This problem can be eliminated by minimizing the gap between the thin glass and the carrier and by providing sufficient adhesion or controlled engagement in such regions 50 between the carrier 20 and the thin glass 10. As exemplified by the examples of Examples 2a, 2e, 3a, 3b, 4c, 4d, 4e and Table 5, the surface modifying layer of the bonding surface (including the material and any associated heat treatment control bonding energy) to provide the sheet 20 Sufficient engagement between the glass-engaging surface and the glass surface on the carrier 10 to avoid such unwanted vibrations in the controlled joint region.

Subsequently, during extraction with the desired portion 56 of the perimeter 57, the portion of the sheet 20 that is within the perimeter 52 can be simply separated from the carrier 10 after processing and after separation of the sheet along the perimeter 57. Because the surface modifying layer controls the bonding energy to prevent the sheet from permanently engaging the carrier, it can be used in the temperature 600 ° C process. Of course, although these surface modifying layers can be The bonding surface energy is controlled during processing at a temperature of 600 ° C. The surface modifying layers can also be used to create a sheet and carrier combination that is resistant to processing at lower temperatures and can be used in such lower temperature applications. In addition, where the heat treatment of the article will not exceed 400 ° C, such as by the examples of Examples 2c, 2d, 4b, Tables 7-11 (including the examples discussed in the alternatives to the examples of Table 10), Example 12a, 12b, 12c, 12g, 12g and examples of surface treatment with separate O2, the surface modifying layer can also be used in the same way - in some cases, depending on other process requirements - to control the bonding surface energy .

Used to provide the joint area

A third use of controlled bonding via a surface modifying layer (including heat treatment of the material and any associated bonding surfaces) is to provide a joint region between the glass carrier and the glass sheet. Referring to FIG. 6, the glass sheet 20 can be joined to the glass carrier 10 by the joint region 40.

In one embodiment of the third use, the joint region 40, the carrier 10, and the sheet 20 can be covalently bonded to each other such that they act as a single piece. In addition, there is a controlled joint region 50 having a perimeter 52 in which the carrier 10 and the sheet 20 are joined to each other, sufficient to withstand handling, and even after high temperature processing, such as in After treatment at a temperature of 600 ° C, the separation of the sheet from the carrier is still allowed. Thus, as exemplified by Examples 1a, 1b, 1c, 2b, 2c, 2d, 4a, 4b, 12d, 12e, 12f, 12h and 12i above, surface modifying layer 30 (including material and bonding surface heat treatment) can be used A joint region 40 is provided between the carrier 10 and the sheet 20. Specifically, such surface modifying layers and heat treatments can be formed on the carrier 10 or outside the perimeter 52 of the controlled bonding region 50 on the sheet 20. Thus, when the article 2 is processed at a high temperature, or treated at a high temperature to form a covalent bond, the carrier and sheet 20 will be joined to each other within the joint region 40 outside the region bounded by the perimeter 52. . Subsequently, during the extraction of the desired portion 56 having the perimeter 57, when the sheet 20 and the carrier 10 need to be diced, the article can be separated along the line 5 because the surface modifying layer and heat treatment combine the sheet 20 with the carrier 10. The valence is bonded so that the sheet 20 and the carrier 10 act as a single piece in this region. Because the surface modifying layer provides permanent covalent bonding of the sheet to the carrier, it can be used in the temperature 600 ° C process. In addition, the heat treatment of the initial formation of the heat treatment or joint region 40 of the article will be In the case of 400 ° C but less than 600 ° C, the surface modifying layer can also be used in the same manner as exemplified by the materials and heat treatment in Example 4a.

In a second embodiment of the third use, in the joint region 40, the carrier 10 and the sheet 20 can be joined to each other by controlled engagement via various surface modifying layers as described above. In addition, there is a controlled joint region 50 having a perimeter 52 in which the carrier 10 and the sheet 20 are joined to each other, sufficient to withstand handling, and even after high temperature processing, such as in After treatment at a temperature of 600 ° C, the separation of the sheet from the carrier is still allowed. Thus, if the treatment would be performed at temperatures up to 600 ° C and there is no need for permanent bonding or covalent bonding in region 40, as by Examples 2e, 3a, 3b, 4c, 4d, 4e and Table 5 above As exemplified by the example, surface modifying layer 30 (including material and bonding surface heat treatment) can be used to provide bonding region 40 between the glass bonding surface of carrier 10 and the glass bonding surface of sheet 20. Specifically, such surface modifying layers and heat treatments can be formed outside of the perimeter 52 of the controlled bonding region 50 and can be formed on or on the carrier 10. The controlled bonding region 50 may be formed using the same or different surface modifying layer as the surface modifying layer formed in the bonding region 40. Alternatively, if the treatment will be performed at a temperature of only up to 400 ° C and there is no need for permanent bonding or covalent bonding in the region 40, as by the above examples 2c, 2d, 2e, 3a, 3b, 4b, 4c, 4d, 4e, examples of Table 5, examples of Tables 7-11 (including the examples discussed in the alternatives to the examples of Table 10), Examples 12a, 12b, 12c, 12g, 12g and the surface using a separate O2 As exemplified by the processing example, surface modifying layer 30 (including material and bonding surface heat treatment) can be used to provide bonding region 40 between the glass bonding surface of carrier 10 and the glass bonding surface of sheet 20.

In a controlled engagement in the replacement region 50, there may be a non-joining region in the region 50, wherein the non-joining region may be an area having increased surface roughness as described in US '727, or as exemplified by Example 2a, It can be provided by a surface modification layer.

For overall annealing or overall processing

The fourth use of the controlled bonding of the above methods is for the overall annealing of the glass sheet stack. Annealing is a thermal process used to achieve compaction of the glass. Compaction involves reheating the glass body to a temperature below the glass softening point, but above the highest temperature reached in subsequent processing steps. This is done before the follow-up and not Structural rearrangement and size relaxation are achieved in the glass during subsequent processing. Annealing prior to subsequent processing is beneficial to maintain precise alignment and/or flatness in the glass body during subsequent processing, as is the case with flat panel display devices where structures made up of many layers need to be tightly tightly bound Alignment, even after exposure to high temperature environments. If the glass is compacted in a high temperature process, the layers of the structure deposited on the glass prior to the high temperature process may not be properly aligned with the layers of the structure deposited after the high temperature process.

Compacting the stacked glass sheets is economically attractive. However, this necessitates staggering or separating adjacent sheets in order to avoid sticking. At the same time, it is beneficial to maintain the sheet extremely flat and optically pleasing, or a pristine surface finish system. In addition, for certain stacks of glass sheets (e.g., sheets having a small surface area), it may be beneficial to "stick" the glass sheets together during the annealing process so that they can be easily moved as a unit without Separation, but easy to separate from each other after the annealing process (by separation, for example, by peeling), so that the sheet can be used alone. Alternatively, it may be beneficial to anneal the stack of glass sheets, wherein the selected glass sheets in the glass sheets are prevented from permanently joining each other while, at the same time, allowing the other of the glass sheets or portions of their other glass sheets (eg, Peripheral) permanently joined to each other. As a further alternative, it may be beneficial to stack the sheets of glass to integrally and selectively permanently engage the perimeter of a selected pair of adjacent sheets in the stack. The controlled engagement of the above-described manner between the sheets of glass can be used to achieve the aforementioned integral annealing and/or selective joining. To control the bonding at any particular interface between adjacent sheets, a surface modifying layer can be used on at least one of the major surfaces facing the interface.

One embodiment of a stack of glass sheets suitable for integral annealing or integral permanent bonding in selected regions (e.g., around the perimeter) will be described with reference to Figures 7 and 8. Wherein, Figure 7 is a schematic side view of a stack 760 of glass sheets 770-772, and Figure 8 is an expanded view thereof for further explanation.

The stack of glass sheets 760 can include glass sheets 770-772 and a surface modifying layer 790 that are used to control the bonding between the glass sheets 770-772. Additionally, stack 760 can include cover sheets 780, 781 disposed on the top and bottom of the stack, and can include a surface modifying layer 790 between the cover material and the adjacent glass sheets.

As shown in FIG. 8, each of the glass sheets 770-772 includes a first major surface 776 and a second major surface 778. The glass sheet can be made of any suitable glass material such as aluminosilicate glass, borosilicate glass or aluminoborosilicate glass. Alternatively, the glass may be alkali metal-containing or may be alkali metal-free. Each of the glass sheets 770-772 can have the same composition, or the sheets can have different compositions. Additionally, the glass sheet can be of any suitable type. That is, for example, the glass sheets 770-772 may all be the carriers as described above, and may all be sheets as described above, or may alternatively be carriers and sheets. It is beneficial to obtain a stack of carriers and a separate stack of sheets when the overall annealing requires different time-temperature cycles for the carrier and for the sheets. Alternatively, in the case of the correct surface modifying layer material and placement, it may be desirable to obtain a stack of alternating carriers and sheets, whereby pairs of carriers and sheets (i.e., forming objects) are needed when needed. The carriers and sheets can be covalently bonded to each other as a whole for later processing while preserving the ability of adjacent objects to separate from one another. Additionally, any suitable number of glass sheets can be present in the stack. That is, despite only three glass pieces 770-772 Shown in Figures 7 and 8, but any suitable number of glass sheets can be included in stack 760.

In any particular stack 760, any of the glass sheets may not include a surface modifying layer, include one surface modifying layer, or include two surface modifying layers. For example, as shown in FIG. 8, sheet 770 does not include a surface modifying layer, sheet 771 includes a surface modifying layer 790 on its second major surface 778, and sheet 772 includes two surface modifying layers 790. One such surface modifying layer is on each of its major surfaces 776, 778.

The cover sheets 780, 781 can be any material that is suitably tolerant (e.g., not only in terms of time and temperature, but also relative to other considerations such as outgassing) to the time-temperature cycle of the customized process. Advantageously, the cover sheet can be made of the same material as the glass sheet being treated. The surface modifying layer 790 may be included in the glass sheet 771 and cover as appropriate when the cover sheets 780, 781 are present and have material that is undesirably bonded to the glass sheet during a given time-temperature cycle after being placed in a stack. Between sheets 781, and/or included between glass sheet 772 and cover sheet 780. When present between the cover material and the glass sheet, the surface modifying layer can be on the cover material (as indicated by the cover material 781 and the adjacent sheet 771), and can be on the glass sheet (eg, the cover material 780 and the sheet material) 772), or may be on both the cover material and the adjacent sheets (not shown). Alternatively, if cover sheets 780, 781 are present, but have materials that will not engage adjacent sheets 772, 772, surface modifying layer 790 need not be present therebetween.

There is an interface between adjacent sheets in the stack. For example, an interface is defined between adjacent sheets of glass sheets 770-772, that is, there is an interface 791 between the sheet 770 and the sheet 771, and an interface 792 exists between the sheet 770 and the sheet 772. In addition, when the cover sheets 780, 781 are present, the cover material 781 and the sheet 771 There is an interface 793 between there, and an interface 794 exists between the sheet 772 and the cover 780.

To control the bonding at a given interface 791, 792 between adjacent glass sheets or at a given interface 793, 794 between the glass sheet and the cover sheet, a surface modifying layer 790 can be used. For example, as shown, at each of the interfaces 791, 792, a surface modifying layer 790 is present on at least one of the major surfaces facing the interface. For example, for interface 791, second major surface 778 of glass sheet 771 includes a surface modifying layer 790 to control the bond between sheet 771 and adjacent sheet 770. Although not shown, the first major surface 776 of the sheet 770 can also include a surface modifying layer 790 thereon to control engagement with the sheet 771, that is, each of the major surfaces facing any particular interface. There is a surface modification layer on it.

A particular surface modifying layer 790 at any given interface 791-794 (and any associated surface modification treatment - for example, heat treatment of a surface prior to application of a particular surface modifying layer to a particular surface, or The surface heat treatment of the surface in contact with the modifying layer can be selected for facing the major surfaces 776, 778 of the particular interface 791-794 to control the bonding between adjacent sheets, and thereby achieve the The desired result of the time-temperature cycle.

If it is desired to integrally anneal the stack of glass sheets 770-772 at a temperature of up to 400 ° C and separate each of the glass sheets from each other after the annealing process, the bonding at any particular interface, such as interface 791, may be used according to the following The materials of any of the examples are controlled along with any associated surface preparation: Examples 2a, 2c, 2d, 2e, 3a, 3b, 4b-4e, Examples of Table 5, Examples of Tables 7-11 (including Table 10) Examples discussed in the alternatives to the examples), Examples 12a, 12b, 12c, 12g, 12g or examples of surface treatment with separate O2. More specifically, the first surface 776 of the sheet 770 will be treated as "thin glass" in Table 2-4, and the second surface 778 of the sheet 771 will be as "carrier" in Table 2-4. Processing, or vice versa. A suitable time-temperature cycle with a temperature of up to 400 °C can then be selected based on the desired degree of compaction, the number of sheets in the stack, and the size and thickness of the sheet to achieve the necessary time-temperature throughout the stack.

Similarly, if it is desired to integrally anneal the stack of glass sheets 770-772 at temperatures up to 600 ° C and separate each of the glass sheets from each other after the annealing process, the bonding at any particular interface, such as interface 791 , may be The examples of Examples 2a, 2e, 3a, 3b, 4c, 4d, 4e or Table 5 were controlled using materials according to any of the examples below, along with any associated surface preparation. More specifically, the first surface 776 of the sheet 770 will be treated as "thin glass" in Table 2-4, and the second surface 778 of the sheet 771 will be as "carrier" in Table 2-4. Processing, or vice versa. A suitable time-temperature cycle with a temperature of up to 600 °C can then be selected based on the desired degree of compaction, the number of sheets in the stack, and the size and thickness of the sheet to achieve the necessary time-temperature throughout the stack.

In addition, it is possible to perform bulk annealing and overall object formation by appropriately arranging the stack of sheets and the surface modifying layer between each pair of sheets. If it is desired to integrally anneal the stack of glass sheets 770-772 at a temperature of up to 400 ° C, and then a pair of adjacent sheets are integrally covalently bonded to each other to form article 2, suitable materials and associated surface preparation may be Select to control the joint. For example, around the perimeter (or at other desired junction regions 40), the following may be used to control the boundary between one of the articles 2 to be formed between the glass sheets (e.g., sheets 770 and 771). Bonding at the face: (i) around the perimeter of the sheets 770, 771 (or other desired joining regions 40), according to materials of any of the examples below, along with any associated surfaces: Examples 2c, 2d, 4b, Table 7 Examples of -11 (including the examples discussed in the alternatives to the examples of Table 10), examples 12a, 12b, 12c, 12g, 12g or examples of surface treatment with separate O2; and (ii) at sheet 770, The inner region of 771 (i.e., inside the region of the periphery treated in (i), or in the desired controlled joint region 50 where one sheet is separated from the other sheet), according to the following example The material of any of the examples was prepared along with any associated surface preparation: Examples 2a, 2e, 3a, 3b, 4c, 4d, 4e or Table 5. In this case, the device processing in the controlled junction region 50 can then be performed at temperatures up to 600 °C.

The materials and heat treatment can be appropriately selected in accordance with the compatibility of each other. For example, any material of material 2c, 2d or 4b can be used for the joint region 40 with the material for the controlled joint region according to Example 2a. Alternatively, the heat treatment for the joint region and the controlled joint region may be appropriately controlled to minimize the effect of heat treatment in a region that adversely affects the degree of bonding in the adjacent region.

After appropriately selecting the surface modifying layer 790 for the glass sheets in the stack and the associated heat treatment, the sheets may be suitably placed in the stack and then heated to 400 ° C to integrally anneal all of the sheets in the stack And the sheets are not permanently joined to each other. Subsequently, the stack may be heated up to 600 ° C to form a covalent bond in the desired joint region of a pair of adjacent sheets, thereby forming an article 2 having a pattern of the joint region and the controlled joint region. The materials of Examples 2a, 2e, 3a, 3b, 4c, 4d, 4e, Table 5 and associated heat treatment can be used to control To form a joint at the interface between one of the articles 2 and the other of the sheets forming the individual but adjacent articles 2 by covalent bonding of the bonding regions 40 so that adjacent objects 2 Will not co-bond with each other. In the same manner as controlling the engagement between adjacent objects, the engagement between the article and the cover sheets present in the stack can be controlled.

Additionally, similar to the above, it is possible to integrally form the article 2 from the stack 760 without pre-annealing the same stack 760. Instead, the sheets may have been annealed independently, or annealed and separated in different stacks, after which the sheets are configured for the overall controlled living piece for the desired controlled joint in the stack. The overall annealing is simply omitted, according to the overall annealing just described above and then integrally forming the article from the same stack.

Although the manner of bonding at the control interface 791 is only explained in detail above, it is of course possible to perform the same control at the interface 792 or any other interface that may be present in a particular stack - such as more than three glass sheets in a stack Condition, or as in the case of a cover sheet that would undesirably bond to the glass sheet. In addition, the same manner of controlling the joint can be used at any of the interfaces 791, 792, 793, 794 present, but different ways of controlling the bonding described above can also be used at different interfaces to produce the same for the type of joint desired. Or different results.

In the above process of integrally annealing or integrally forming the article 2, when the HMDS is used as a material for controlling the bonding at the interface, and the HMDS is exposed to the periphery of the stack, it should be covalently bonded in the region where it is desired to prevent the HMDS. At the time, heating of about 400 ° C or more is performed in an oxygen-free atmosphere. That is, if the HMDS is exposed to the atmosphere, it is sufficient to oxidize a certain amount of oxygen in the HMDS (above about 400 ° C). At the temperature, the bond in any such region where the HMDS has oxidized will become a covalent bond between adjacent glass sheets. Other alkyl hydrocarbon decanes can similarly be exposed to oxygen at elevated temperatures (e.g., above about 400 ° C) such as ethyl, propyl, butyl or steryl decane. . Similarly, if other materials are used for the surface modification layer, the environment for the overall annealing should be selected so that the material does not degrade during the time-temperature cycle of the annealing. As used herein, oxygen free may mean an oxygen concentration of less than 1000 ppm by volume, more preferably less than 100 ppm by volume.

Once the stack of sheets has been annealed, the individual sheets can be separated from the stack. Individual sheets can be processed (for example, by oxygen plasma, at The surface modifying layer 790 is removed by heating in an oxygen atmosphere at a temperature of 400 ° C or by chemical oxidation, SC1 or SC2). Individual sheets can be used, for example, as an electronic device substrate, such as an OLED, FPD or PV device, as desired.

The above method of integral annealing or overall treatment has the advantage of maintaining the surface of the cleaning sheet economically. More specifically, the sheet does not need to be maintained in a clean environment throughout, such as in a clean room annealing kiln. Instead, the stack can be formed in a clean environment and subsequently processed in a standard annealing kiln (ie, an annealing kiln where the cleanliness is not controlled), while the sheet surface is not soiled by particles because of the sheet There is no fluid flow between them. Thus, the surface of the sheet is protected from the stacking of the sheets in the environment in which it is annealed. After annealing, the stack of sheets can be easily transported to another processing area (in the same facility or in different facilities) because the sheets maintain a certain degree of adhesion, but remain separated from each other with sufficient force without damaging the sheets. That is, the glass manufacturer, for example, can assemble and anneal the stack of glass sheets and then ship the sheets as a stack, where during shipment The sheets are held together (without concern that they are separated during transport), and after reaching their destination, the sheets can be separated from the stack by the consumer, who can use the sheets individually or in smaller groups To use the sheet. Once separation is required, the stack of sheets can be processed again in a clean environment (if necessary after washing the stack).

Example of overall annealing

The glass substrate is used in a state of being received from the fusion drawing drawing process. The molten drawn glass composition was (in % by mole): SiO2 (67.7), Al2O3 (11.0), B2O3 (9.8), CaO (8.7), MgO (2.3), SrO (0.5). Seven (7) 0.7 mm thick by 150 mm diameter melt drawn drawn glass substrates were patterned by lithography using a 200 nm deep reference point/cursor using HF. Two (2) nm plasma-deposited fluoropolymer is applied as a surface modification layer on all the bonding surfaces of all the glass substrates, that is, the coated substrate faces each surface of the other substrate, and thereafter, each The resulting surface energy of the sheet surface was approximately 35 mJ/m2. Seven coated individual glass substrates are placed together to form a single, thick substrate (referred to as a "glass stack"). The glass stack was annealed from a 30 ° C ramp to 590 ° C over a period of 15 minutes in a nitrogen purge tube furnace, held at 590 ° C for 30 minutes, then ramped down to about 230 ° C over a 50 minute period, and then the glass was stacked from the furnace Remove and cool to room temperature of about 30 ° C in about 10 minutes. After cooling, the substrate is removed from the furnace and is easily separated into individual sheets using a razor wedge (i.e., the sample is not permanently joined, generally or partially). Compaction was measured for each individual substrate by comparing the glass reference point to a non-annealed quartz reference. Individual substrates were found to be about 185 ppm tight. Both of the substrates were subjected to a second annealing cycle (590 ° C / hold for 30 minutes) as described above as individual samples (not stacked together). Re-measure the compaction and find the substrate Since the second heat treatment is further tightened to less than 10 ppm (actually 0 to 2.5 ppm) (the glass size change after the second heat treatment - compared to the original glass size - minus the glass size change after the first heat treatment). Accordingly, the inventors have demonstrated that individual glass sheets can be coated, stacked, heat treated at elevated temperatures to achieve compaction, cooling, separation into individual sheets, and have dimensional changes of <10 ppm and even <ppm after the second heat treatment. (compared to its size after the first heat treatment).

Although the furnace in the above annealing example is flushed with nitrogen, the annealing furnace may be flushed with other gases including air, argon, oxygen, CO2 or a combination thereof depending on the annealing temperature and the material of the surface modifying layer in a specific environment. Stability at equal temperatures. Instead of an inert atmosphere, the furnace in the above annealing may be a vacuum environment.

In addition, although not shown, the glass may be annealed in the form of a roll instead of a sheet. That is, a suitable surface modifying layer can be formed on one or both sides of the glass ribbon and then rolled into a strip. The entire reel can be subjected to the same treatment as indicated above for the sheet, after which the glass of the entire reel is annealed without bonding a wrap of glass to the adjacent cladding material. After unfolding, the surface modifying layer can be removed by any suitable process.

Degassing

Polymer adhesives used in typical wafer bonding applications are typically 10-100 microns thick and lose about 5% of their mass at or near their temperature limits. For such materials that escape from thick polymer films, it is easy to quantify the amount of mass loss or outgassing by mass spectrometry. On the other hand, it is more challenging to measure outgassing from thin surface treatments of about 10 nm thick or less, such as the plasma polymer or self-assembled monolayer surface modifying layer described above, And a thin layer of pyrolysis oil. Mass spectrometry is not sensitive enough for these materials. However, there are many other ways to measure outgassing.

The first way to measure small outgassing is based on surface energy measurements and will be described with reference to Figure 9. For this test, the settings as shown in Figure 9 can be used. The first substrate or carrier 900 having the surface modifying layer to be tested has a surface 902, that is, a surface modifying layer corresponding to the surface modifying layer 30 to be tested in composition and thickness. The second substrate or cover member 910 is placed such that its surface 912 abuts the surface 902 of the carrier 900 but is not in contact therewith. Surface 912 is the uncoated surface, i.e., the surface of the bare material from which the cover material is formed. The spacers 920 are placed at various points between the carrier 900 and the cover member 910 to hold them in spaced relation to each other. The spacer 920 should be thick enough to separate the cover material 910 from the carrier 900, allowing the material to move from one to the other, but thin enough to minimize contamination of the surfaces 902 and 912 from the chamber atmosphere during testing. The amount. The carrier 900, the spacer 920, and the cover member 910 together form the test article 901.

Prior to assembly of the test article 901, the surface energy of the bare surface 912, such as the surface energy of the surface 902 (i.e., the surface of the carrier 900 having the surface modifying layer provided thereon), is measured. The surface energy, that is, the polar component and the dispersed component, as shown in Fig. 10, was measured by fitting the Wu model to the contact angles of three test liquids; water, diiodomethane, and hexadecane.

After assembly, the test article 901 is placed in the heating chamber 930 and heated via a time-temperature cycle. Heating is carried out under atmospheric pressure and under flowing N2 gas, i.e., at a rate of 2 standard liters per minute in the direction of arrow 940.

The surface 902 changes during the heating cycle (eg, including surface modification layers due to evaporation, pyrolysis, decomposition, polymerization, reaction with the carrier, and de-wetting) by surface energy of surface 902 Change to prove. The change in surface energy itself of surface 902 does not necessarily mean that the surface modifying layer has been degassed, but indicates the overall instability of the material at its temperature, as its properties vary due to, for example, the mechanisms indicated above. Therefore, the smaller the surface energy change of the surface 902, the more stable the surface modifying layer. On the other hand, due to the closeness of surface 912 to surface 902, any material that degases from surface 902 will collect on surface 912 and will change the surface energy of surface 912. Thus, the surface energy of surface 912 varies as a proxy for outgassing of the surface modifying layer present on surface 902.

Therefore, one test for degassing uses a change in surface energy of the cover material surface 912. To be precise, if the surface energy - the surface energy of surface 912 - changes At 10 mJ/m2, there is degassing. This amount of surface energy change is consistent with contamination that can result in loss of film adhesion or degradation of material properties and device performance. The surface energy change of 5mJ/m2 is close to the repeatability of surface energy measurement and the heterogeneity of surface energy. This small change is consistent with minimal degassing.

During the test that produced the results in FIG. 10, the carrier 900, the cover material 910, and the spacer 920 were all made of Eagle XG glass, which is an alkali-free metal available from Corning Incorporated, Corning, NY. Aluminium borosilicate displays grade glass, although this is not required. The carrier 900 and the cover member 910 are 150 mm in diameter and 0.63 mm thick. Typically, carrier 910 and cover material 920 will be made of the same material as carrier 10 and sheet 20, respectively, requiring a degassing test of the material. During this test, the septum is 0.63mm thick and 2mm The width and length are 8 cm, and a gap of 0.63 mm is formed between the surface 902 and the surface 912. During this test, chamber 930 was incorporated into the MPT-RTP 600s rapid thermal processing equipment, which was cycled from room temperature to the test limit temperature at a rate of 9.2 ° C per minute; the chamber was maintained at the test limit temperature as in the chart. The change time indicated by "annealing time" was followed by cooling to 200 ° C at the furnace rate. After the oven has cooled to 200 ° C, the test article is removed, and after the test article has cooled to room temperature, the surface energy of each surface 902 and surface 912 is again measured. Thus, for example, in the case of using the material of the material surface change of material #1, line 1003 (testing to the extreme temperature of 450 ° C), the data is collected as follows. The surface energy at 75 minutes shows the surface energy of 75 mJ/m2 (millijoules per square meter) and is the surface energy of the bare glass, that is, the time-temperature cycle has not been run. The data point at one minute indicates the surface energy measured after the time-temperature cycle performed as follows: Object 901 (having material #1, which is used as a surface modifying layer on the carrier 900 to present the surface 902) Placed in a heating chamber 930 at room temperature and atmospheric pressure; in the case of an N2 gas stream at two standard liters per minute, the chamber is heated to a test limit temperature of 450 ° C at a rate of 9.2 ° C per minute, and Hold at a test limit temperature of 450 ° C for 1 minute; then cool the chamber to 300 ° C at a rate of 1 ° C per minute, and then remove the article 901 from the chamber 930; then cool the object to room temperature (no N2 Flow atmosphere); the surface energy of surface 912 is then measured and plotted as a point on line 1003 for 1 minute. The remaining data points (lines 1003, 1004) of material #1, and material #2 were then determined in a similar manner using the annealing time corresponding to the retention time for several minutes at the test limit temperature (450 ° C or 600 ° C as appropriate). (lines 1203, 1204), material #3 (lines 1303, 1304), material #4 (lines 1403, 1404), Material #5 (line 1503, 1504), material #6 (lines 1603 and 1604) and material #7 (lines 1703, 1704) data points. Lines 1001, 1002, 1201, 1202, 1301, 1302, 1401, 1402, 1501, 1502, 1601, 1602, 1701, and 1702 representing the surface energy of the surface 902 of the corresponding surface modifying layer material (material #1-7) The data points were determined in a similar manner with the exception that the surface energy of surface 902 was measured after each time-temperature cycle.

As described below, the above assembly process and time-temperature cycle were performed on seven different materials, and the results are plotted in Figure 10. Among the seven materials, materials #1-4 and 7 correspond to the surface modifying layer materials described above. Materials #5 and #6 are comparative examples.

Material #1 is a CHF3-CF4 plasma polymerized fluoropolymer. This material is consistent with the surface modifying layer of Example 3b above. As shown in Figure 10, lines 1001 and 1002 show that the surface energy of the carrier does not change significantly. Therefore, this material is extremely stable at temperatures from 450 ° C to 600 ° C. In addition, as shown by lines 1003 and 1004, the surface energy of the cover material does not change significantly, that is, changes to 5mJ/m2. Therefore, there is no outgassing associated with this material from 450 ° C to 600 ° C.

Material #2 was phenyl decane, which was a self-assembled monolayer (SAM) deposited from a 1% toluene solution of phenyltriethoxynonane and cured in a vacuum oven at 190 °C for 30 minutes. This material is consistent with the surface modifying layer of Example 4c above. As shown in Figure 10, lines 1201 and 1202 indicate some variation in surface energy on the carrier. As noted above, this indicates some variation in the surface modification layer, and in comparison, material #2 is slightly less stable than material #1. However, as shown by lines 1203 and 1204, the surface energy of the carrier changes to 5 mJ/m2, confirming that no change in the surface modification layer produces degassing.

Material #3 was pentafluorophenyl decane, which was deposited from a 1% toluene solution of pentafluorophenyltriethoxydecane and cured in a vacuum oven at 190 ° C for 30 minutes. This material is consistent with the surface modifying layer of Example 4e above. As shown in Figure 10, lines 1301 and 1302 indicate some variation in surface energy on the carrier. As noted above, this indicates some variation in the surface modification layer, and in comparison, material #3 is slightly less stable than material #1. However, as shown by lines 1303 and 1304, the surface energy of the carrier changes to 5 mJ/m2, confirming that no change in the surface modification layer produces degassing.

Material #4 was hexamethyldioxane (HMDS) which was self-vapor deposited in a YES HMDS oven at 140 °C. This material is consistent with the surface modifying layer of Example 2b of Table 2 above. As shown in Figure 10, lines 1401 and 1402 indicate some variation in surface energy on the carrier. As noted above, this indicates some variation in the surface modification layer, and in comparison, material #4 is slightly less stable than material #1. In addition, the surface energy variation of the carrier of material #4 is greater than the variation of any of materials #2 and #3, and the indicator material #4 is slightly unstable compared to materials #2 and #3. However, as shown by lines 1403 and 1404, the surface energy of the carrier changes to 5 mJ/m2, which confirmed that the change of the surface modification layer did not affect the degassing of the surface energy of the cover material. However, this is consistent with the manner in which HMDS is degassed. That is, HMDS degass ammonia and water, and the ammonia and water do not affect the surface energy of the cover material, and may not affect some electronic equipment manufacturing equipment and/or processing. On the other hand, there may be other problems when the degassed product is trapped between the sheet and the carrier, as indicated below in connection with the second outgassing test.

Material #5 is glycidoxypropyl decane, which is a SAM deposited from a 1% toluene solution of glycidoxypropyl triethoxy decane and cured in a vacuum oven at 190 ° C for 30 minutes. This is a comparative example material. Although there is a relatively small change in the surface energy of the carrier, as indicated by lines 1501 and 1502, there is a significant change in the surface energy of the cover material, as indicated by lines 1503 and 1504. That is, although material #5 is relatively stable on the surface of the carrier, it does degas a significant amount of material on the surface of the cover material, whereby the surface energy of the cover material changes. 10mJ/m2. Although the surface energy was within 10 mJ/m 2 at the end of 10 minutes at 600 ° C, the change during the period of time did exceed 10 mJ/m 2 . See, for example, the data points at 1 minute and 5 minutes. Although not wishing to be bound by theory, a slight increase in surface energy from 5 minutes to 10 minutes may be associated with some outgassing materials that decompose and fall from the surface of the cover material.

Material #6 is DC704, which was dispensed onto the vehicle by dispensing 5 ml of Dow Corning 704 diffusion pump oil tetramethyltetraphenyltrioxane (available from Dow Corning) and placed in air at 500. The polyfluorene oxide coating prepared on a hot plate for 8 minutes on a °C hot plate. It can be seen that the end of the smoke indicates the completion of the sample preparation. After preparing the sample in the above manner, the degassing test described above was carried out. This is a comparative example material. As shown in Figure 10, lines 1601 and 1602 indicate some variation in surface energy on the carrier. As noted above, this indicates some variation in the surface modification layer, and in comparison, material #6 is slightly less stable than material #1. In addition, as shown by lines 1603 and 1604, the surface energy of the carrier changes. 10 mJ/M2, confirming significant degassing. More specifically, at a test limit temperature of 450 ° C, the 10 minute data point shows a reduction in surface energy of about 15 mJ/m 2 and an even greater surface energy reduction at points of 1 minute and 5 minutes. small. Similarly, at the 10 minute data point, the surface energy of the cover material is reduced to about 25 mJ/m2 at a 10 minute data point, slightly greater at 5 minutes, in terms of surface energy change of the cover material during the cycle at 600 °C test limit temperature. And slightly smaller in 1 minute. All in all, despite this, a significant amount of degassing of this material was confirmed throughout the test.

Material #7 is a CH4-H2 plasma deposited polymer which is sequentially treated with a short period of N2-O2 and N2 plasma. This material is similar to the surface modifying layer in the examples of Table 11 above. As shown in Figure 10, lines 7001 and 7002 show that the surface energy of the carrier does not change significantly. Therefore, this material is extremely stable at temperatures from 450 ° C to 600 ° C. In addition, as shown by lines 7003 and 7004, the surface energy of the cover material does not change significantly, that is, changes to 5mJ/m2. Therefore, there is no outgassing associated with this material from 450 ° C to 600 ° C.

Significantly, for materials #1-4 and 7, the surface energy of the entire time-temperature cycle indicates that the surface energy of the surface of the cover material remains the same as that of the bare glass, that is, the surface of the self-carrier is not collected. Degassing material. In the case of material #4, as indicated in conjunction with Table 2, the manner in which the surface of the carrier and the surface of the sheet are prepared in the manner in which the article (the sheet is bonded to the carrier via the surface modifying layer) will be large in terms of preservation in FPD processing. The difference. Thus, although the example of material #4 shown in FIG. 10 may not degas, this material may or may not be preserved in the 400 ° C or 600 ° C test, as indicated in connection with the discussion of Table 2.

The second way of measuring a small amount of outgassing is based on the assembled article, that is, the article in which the sheet is bonded to the carrier via the surface modifying layer, and the percentage change in the area of the bubble is used to determine the outgassing. That is, during heating of the article, bubbles formed between the carrier and the sheet indicate degassing of the surface modifying layer. As indicated above in connection with the first outgassing test, it is difficult to measure the outgassing of the extremely thin surface modifying layer. In this second test, the outgassing under the sheet can be limited by the strong adhesion between the sheet and the carrier. despite this, A 10 nm thick layer (eg, plasma polymer material, SAM, and pyrolytic oil surface treatment) can still generate bubbles during heat treatment regardless of its small absolute mass loss. Moreover, the creation of bubbles between the sheet and the carrier can cause problems in patterning, photolithography, and/or alignment during processing of the device on the sheet. Additionally, blistering at the boundary of the bond area between the sheet and the carrier can cause problems with downstream process variations from process flow of one process. A 5% change in bubble area is significant (indicating degassing) and is not desirable. on the other hand, The change in bubble area of 1% is not significant and indicates that there is no outgassing.

The average bubble area of the bonded thin glass using manual bonding in a Class 1000 clean room was 1%. The % bubble in the bonding carrier varies with the cleaning of the carrier, the thin glass sheet, and the surface preparation. Since these initial defects act as nucleation sites for bubble growth after heat treatment, any change in bubble area of less than 1% after heat treatment is within the variability of sample preparation. For this test, a commercially available desktop scanner (Epson Expression 10000XL Photo) with a transparency unit was used to obtain a first scanned image of the area where the sheet and the carrier were joined immediately after bonding. Each part was scanned using standard Epson software using 508 dpi (50 micron/pixel) and 24-bit RGB. The image processing software first prepares the image by stitching the images of different segments of the sample into a single image as needed, and removing the scanner artifacts (by using the sample without the sample in the scanner) Calibration reference scan). The joint area is then analyzed using standard image processing techniques such as sizing, hole filling, erosion/expansion, and binary large blob analysis. The new Epson Expression 11000XL Photo can also be used in a similar manner. In the transmissive mode, the bubbles in the joint region are visible in the scanned image and the value of the bubble area can be determined. Subsequently, the bubble area is compared to the total joint area (i.e., the total overlap area between the sheet and the carrier) to calculate the % area of the bubble in the joint area relative to the total joint area. The samples were then heat treated for up to 10 minutes in a MPT-RTP 600s rapid thermal processing system under N2 atmosphere at 300 ° C, 450 ° C and 600 ° C test limit temperatures. Specifically, the time-temperature cycle performed includes: inserting the article into a heating chamber at room temperature and atmospheric pressure; then heating the chamber to a test limit temperature at a rate of 9 ° C per minute; maintaining the chamber at The test was carried out at a temperature limit of 10 minutes; the chamber was then cooled to 200 ° C at furnace rate; the article was removed from the chamber and allowed to cool to room temperature; the article was then scanned a second time using an optical scanner. The % bubble area from the second scan was then calculated as above and compared to the % bubble area from the first scan to determine the % bubble area change (Δ% bubble area). As indicated above, The 5% bubble area change was significant and indicated degassing. Due to the variability of the original % bubble area, the % bubble area change was chosen as the measurement criterion. That is, most surface modifying layers have a bubble area of about 2% in the first scan due to handling and cleanliness after the sheets and carriers have been prepared and prior to their bonding. However, changes can occur between materials. The same material #1-7 set forth with respect to the first outgassing test method was again used for this second outgassing test method. Of these materials, material #1-4 exhibited approximately 2% bubble area in the first scan, while materials #5 and #6 exhibited significantly larger bubble areas in the first scan, i.e., about 4%.

The results of the second degassing test will be described with reference to Figs. 11 and 12. The results of the degassing test for materials #1-3 and #7 are shown in Fig. 11, and the results of the degassing test for materials #4-6 are shown in Fig. 12.

The result of material #1 is shown in Figure 11 as a square data point. As can be seen from the figure, the % bubble area change is close to zero for the test limit temperatures of 300 ° C, 450 ° C, and 600 ° C. Therefore, material #1 confirmed that there was no outgassing at these temperatures.

The result of material #2 is shown in Figure 11 as a diamond data point. As can be seen from the figure, the % bubble area change is less than 1 for the test limit temperatures of 450 ° C and 600 ° C. Therefore, material #2 confirmed that there was no outgassing at these temperatures.

The result of material #3 is shown in Figure 11 as a triangular data point. As can be seen from this figure, similar to the result of material #1, the % bubble area change is close to zero for the test limit temperatures of 300 ° C, 450 ° C, and 600 ° C. Therefore, material #1 confirmed that there was no outgassing at these temperatures.

The result of material #7 is shown in Figure 11 as a cross-shaped data point. As can be seen from the figure, the % bubble area change is close to zero for the test limit temperatures of 300 ° C and 450 ° C. Therefore, material #7 confirmed that there was no outgassing at these temperatures. For the test limit temperature of 600 ° C, material #7 exhibited a change in bubble area of less than 2%. Therefore, material #7 demonstrates at most a minimum of outgassing at this temperature.

The result of material #4 is shown in Figure 12 as a circular data point. As can be seen from the figure, the % bubble area change is close to zero for the test limit temperature of 300 ° C, but for some samples, it is close to 1% at the test limit temperature of 450 ° C and 600 ° C, and for the same material For the other samples, it was about 5% at the test limit temperatures of 450 ° C and 600 ° C. The results of material #4 are extremely inconsistent and take It depends on the manner in which the sheet surface and the carrier are prepared for bonding using HMDS materials. The manner in which the samples are performed depending on the manner in which the samples are prepared is consistent with the examples and associated discussion of the materials set forth in connection with Table 2 above. It is to be noted that for this material, a sample having a bubble area change of approximately 1% of the 450 ° C and 600 ° C test limit temperatures does not allow the sheet to separate from the carrier according to the separation test set forth above. That is, the strong adhesion between the sheet and the carrier can have limited bubble generation. On the other hand, a sample having a change in bubble area of approximately 5% is allowed to separate the sheet from the carrier. Therefore, a sample that does not have a degassing has a non-desired result of increasing adhesion after the temperature treatment of bonding the carrier and the sheet together (preventing removal of the sheet from the carrier), and allowing removal of the sheet and the sample of the carrier Has the desired result of degassing.

The result of material #5 is shown in Figure 12 as a triangular data point. As can be seen from this figure, the % bubble area change is about 15% for the test limit temperature of 300 ° C and is quite high for the higher test limit temperatures of 450 ° C and 600 ° C. Therefore, material #5 demonstrates significant outgassing at these temperatures.

The result of material #6 is shown in Figure 12 as a square data point. As can be seen from this figure, the % bubble area change exceeds 2.5% for the test limit temperature of 300 ° C and exceeds 5% for the test limit temperatures of 450 ° C and 600 ° C. Thus, material #6 demonstrates significant outgassing at 450 ° C and 600 ° C test limit temperatures.

Bonding the polymer surface to the glass surface

Demonstration of displays on polymer sheets such as polyethylene naphthalate (PEN), polyethylene terephthalate (PET), and polyimide (PI), where the device system The film is made from a sheet of PEN laminated to a glass carrier to a sheet. Up to 100 micron thick layers of polymeric binders are typically used to laminate PEN and PET to glass carriers for sheet to sheet processing. The weight loss of such adhesives during processing of the device is typically greater than 1%, creating a challenge to contamination due to outgassing of the solvent. In addition, complete removal of the adhesive is challenged, so glass carriers are often not reused.

The present application describes the use of a thin surface modifying layer to form a moderate bond between the glass carrier and the polymeric sheet to create a controlled temporary bond that is strong enough to be preserved in the TFT process but weak enough to Allow disengagement. However, thermal, vacuum, solvent, and acidic, and ultrasonic flat panel display (FPD) processes require robust bonding of the thin polymeric sheet to the carrier, but the various surface modifying layers of the surface modifying layer of the present invention discussed herein are capable of This controlled bonding is achieved for processing the polymer sheet on a glass carrier. In addition, the controlled bonding can allow the polymer sheet to be removed from the carrier without catastrophic damage to the polymer sheet or glass carrier, and in turn provide a reusable glass carrier.

Three kinds of transistor technology are used in mass production of FPD backplane fabrication: amorphous germanium (aSi) bottom gate TFT, polycrystalline silicon (pSi) top gate TFT, and amorphous oxide (IGZO) bottom gate TFT . All of these technologies require a high temperature processing step of >300C. This requirement for substrates capable of achieving high temperature processes, as well as requirements for chemical, mechanical, and vacuum compatibility, has become a major limitation of the industrialization of flexible displays on existing flexible substrates such as polymers. The general process begins with the cleaning of the polymer substrate, typically with an ultrasonic or megasonic ultrasonic agitation cleaning in an alkaline solution followed by DI water cleaning. Device structure is based on material deposition and photolithography patterning followed by material etching Made in many subtractive cycles. Metal, dielectric and semiconductor materials are deposited by a vacuum process such as sputtering of metals, transparent conductive oxides and oxide semiconductors; crystallization of amorphous germanium, tantalum nitride and germanium dioxide at elevated temperatures Vapor deposition (CVD) deposition. Laser and flash lamp annealing allows p-Si to crystallize without excessive substrate heating, but uniformity is challenged and performance is poor compared to glass substrates. The layers are patterned by polymer resist and etching followed by photolithographic patterning of resist stripping. A vacuum plasma (dry) etching process and an acid wet etching process are used. In FPD processing, the photoresist is typically stripped by a hot solvent, typically using ultrasonic or megasonic ultrasonic agitation.

Removing the thick layer of adhesive prevents the vehicle from being reusable. For polymer adhesives suitable for FPD treatment, they must have good chemical resistance in solvents, strong acids and strong bases. However, these same properties make removal a challenge. Moreover, in the case of layers up to 100 microns thick, the plasma process is not practical for removing layers. The main challenge in the fabrication of organic thin film transistors is the lamination of thin polymer sheets to carriers.

This application describes a method for controlled temporary bonding of a polymer sheet to a glass carrier for use in an FPD process, and describes a sheet-to-sheet process reusable glass carrier for a thin polymer substrate. The formation of the surface modifying layer on the glass carrier creates a temporary bond with a moderate adhesion between the thin polymer sheet and the carrier. Moderate adhesion is achieved by optimizing the contribution of van der Waals and covalent attraction energy to the total adhesion energy, which is controlled by the polar and non-polar surface energy components of the modulating sheet and the carrier. This moderate bond is strong enough to be preserved in FPD processing (including wet ultrasonic processes, vacuum processes, and thermal processes) and still allows the polymer sheet to remain applied by sufficient peel force And disengaged from the carrier. Debonding allows for the removal of the device fabricated on a thin polymer sheet and the re-use of the carrier because the surface modifying layer is <1 micron thick and is easily removed in the oxygen plasma.

The advantage is obtained that a thin surface modifying layer is used to create a moderate bond between the thin polymer sheet and the glass carrier.

(1) A substantially 100X reduction in the amount of material used to bond a thin polymer sheet to a carrier reduces the outgassing and reduces the likelihood of contamination of the downstream process of absorption and contamination compared to commercial adhesives.

(2) The highly crosslinked plasma polymer surface modification layer is non-volatile and insoluble, thereby reducing the probability of degassing and process contamination.

(3) The surface modifying layer is easily removed at high temperatures in oxygen plasma or downstream oxygen plasma.

(4) The glass carrier can be reused because the surface modifying layer is thin and easy to remove.

PEN and PET are especially typical polymer substrates that can be used in electronic form for reeling. It is relatively chemically inert compared to most polymers, has low water absorption, low expansion, and temperature resistance. However, these properties are inferior to those of glass. For example, the maximum temperature for non-thermally stable PEN is 155 ° C, while the maximum temperature for PET is only 120 ° C. These temperatures are lower than the >600 °C use temperature for display glass suitable for pSi processing. The thermal expansion of PEN is about 20 ppm as opposed to 3.5 ppm of the display glass. Moreover, after 30 min at 150 ° C, the shrinkage at temperature is about 0.1%, which far exceeds the relaxation and compaction of the glass at significantly higher temperatures. These secondary physical properties of the polymer substrate require process adaptation to deposit high quality in high yields. Set. For example, the cerium oxide, cerium nitride, and amorphous germanium deposition temperatures must be lowered to remain within the limits suitable for the polymer substrate.

The above physical properties of the polymer also make it challenging to engage with rigid carriers for sheet-to-sheet processing. For example, the thermal expansion of the polymer sheet is typically greater than the thermal expansion of the display glass by 6x. Although the upper temperature limit is small, the thermal stress is large enough to produce warpage and curvature, and causes delamination when using conventional bonding techniques. The use of high expansion glass such as soda lime or higher expansion metal carriers helps to manage warping challenges, but such carriers are typically challenging relative to contamination, compatibility or roughness (thermal transfer).

The surface energy of PEN and PET is also significantly lower than the surface energy of glass. As shown in Table 16, below, Corning® Eagle XG® glass exhibits a surface energy of approximately 77 mJ/m2 after cleaning with SC1 chemistry and standard cleaning techniques. See example 16e. In the absence of surface treatment, PEN and PET are non-polar and have a surface energy of 43-45 mJ/m2 (43-45 dyn/cm). See Table 15 below, from "Remote Atmospheric-Pressure Plasma Activation of the Surfaces of Polyethylene Terephthalate and Polyethylene Naphthalate", E. Gonzalez, II, MD Barankin, PC Guschl and RF Hicks, Langmuir 2008 24(21), 12636- Table 2 of 12643. The plasma cleaning process (e.g., by oxygen plasma) greatly increases the surface energy to 55-65 mJ/m2 (55-65 dyn/cm, "plasma") by increasing the polarity component. In addition, UV ozone treatment or corona discharge can be used to clean the polymer and temporarily increase its surface energy. However, over time, the surface energy is reduced back to its previous value ("aging").

In the case of such surface energies (about 55 mJ/m2 to about 65 mJ/m2) of the polymer bonding surface and about 77 mJ/m2 of the glass carrier bonding surface, the polymer sheet does not sufficiently bond to the glass carrier to allow The structure is treated on a sheet, but if it is first placed on a glass carrier and then heated to a moderate temperature, the polymer cannot be peeled off from the glass carrier. Thus, to initially bond PEN or PET to the glass at room temperature, it has been found to be beneficial to modify the surface energy of the glass carrier to approximately match the surface energy of PEN or PET. In addition, it has been found that various surface modifying layers of the surface modifying layer control the bonding energy so that the polymer layer can be self-conducted even after the organic-TFT processing cycle (including one hour 120 ° C vacuum annealing and one minute 150 ° C post-baking step). The glass carrier is peeled off.

By properly adjusting the surface energy of the glass carrier by selecting an appropriate surface modifying layer, sufficient wetting strength and adhesion strength can be achieved to controllably bond the polymer, such as PEN or PET, to the glass carrier in a manner that The method is suitable for organic-TFT treatment (including one hour 120 ° C vacuum annealing and one minute 150 ° C post-baking step) while allowing the polymer to be self-removable after treatment. The polymeric sheet can be successfully removed from the carrier, i.e., the polymeric sheet is controllably bonded to the carrier, even after the above treatment, the OTFT on the polymeric sheet and the mask used to create it There is also no significant difference in transistor geometry between the OTFTs. The surface modification layer can be exemplified throughout the specification. Choose from a variety of materials and treatments. The polymeric material may advantageously be plasma cleaned prior to bonding (to increase the polar component of its surface energy to facilitate initial bonding), but need not be so because the surface energy of the glass carrier can be greatly altered in order to achieve A suitable level of controlled engagement with the polymer in the current state (i.e., as received, as in a cleaned state, or as an aged state). Based on the above examples and their examples in Table 16, the surface energy range from about 36 mJ/m2 (Example 5g) to about 80 mJ/m2 (Example 5f) can be obtained on the glass carrier joining surface.

Several of the above methods of surface modification are suitable for adhesive bonding of a polymer sheet to a glass carrier, the surface modification comprising formation from a carbon source, such as their surface modification from plasma polymerization of a hydrocarbon gas. For example: plasma polymer films deposited from fluorocarbon gases (Examples 5a and 5g); plasma polymer films deposited from fluorocarbon gases and subsequently treated with nitrogen and hydrogen (Example 5m); Fluorine gas deposited plasma polymer film (Examples 6a-6j); plasma polymer film deposited from hydrocarbon gas, optionally nitrogen and hydrogen (Examples 7a-g, 12j); deposited from various non-fluorine-containing gases and subsequently a plasma treated plasma polymer membrane (Examples 9a-9j) wherein the surface energies are applicable to polymers in various states of cleanliness and/or aging; and deposition from various non-fluorine-containing gases and subsequent sequence Treatment with nitrogen followed by hydrogen (Examples 10a-10p), or treatment with dilute ammonia (Examples 8b, 8d), or sequentially with N2-O2 followed by N2 (Examples 11a, 11e), or with N2-O2 ( The plasma polymer films of Examples 11f, 12c), all of which would work particularly well with the plasma cleaning PEN. Other surface treatments may be suitable where a polymer other than PET or PEN is used, depending on the surface energy of the polymer just prior to bonding, the degree of cleanability of the polymer, and the ageing process. The surface energy affected by the degree. It has been found that the surface energy of the glass carrier, which approximately matches the surface energy of the polymer sheet, works well both in the initial bonding and in the controlled bonding so that the polymer sheet can be easily handled in an organic-TFT type (including one hour at 120 ° C). The vacuum annealing and the one-minute 150 ° C post-baking step) were followed by debonding.

Additionally, other formulations of the surface modifying layer are probed to achieve surface energy within the energy range of the surface of the polymeric sheet used to bond the polymeric sheet to the glass carrier.

Surface modifying layer formed from a mixture of gases

An example of using a plasma polymer film to adjust the surface energy of the bonding surface and covering the surface hydroxyl groups on the bonding surface and/or controlling the type of polarity bonding on the bonding surface is that the surface modifying layer film is self-contained of a hydrocarbon (eg, methane). Deposition of a mixture of source gases. Deposition of the surface modifying layer can occur at atmospheric or reduced pressure and is performed using plasma excitation, such as DC or RF parallel plates, inductively coupled plasma (ICP), electron cyclotron resonance (ECR), downstream Microwave or RF plasma. The plasma polymerized surface modifying layer can be disposed on the joining surface, the sheet, or both of the carrier. As indicated above in connection with the examples of Table 3, plasma polymerization produces a layer of highly crosslinked material. Control of the reaction conditions and source gases can be used to control the surface modification film thickness, density, and chemistry to tailor the functional groups to be used. The surface energy of the carrier engaging surface can be adjusted by controlling the properties of the film, including controlling the amount of surface hydroxyl groups covered. The surface energy can be adjusted to control the extent of the joint, i.e., to prevent permanent covalent bonding between the sheet and the carrier during subsequent processing to effect placement of the film or structure on the sheet.

In the examples of Table 16 below, various conditions were used to deposit a plasma polymeric film onto a glass carrier. The glass carrier is a substrate made of Corning® Eagle XG® aluminoborosilicate free alkali metal display glass (available from Corning Incorporated, Corning NY). The vehicle is cleaned using SC1 and/or SC2 chemistry and standard cleaning techniques prior to film deposition. Films were deposited in a STS multiplexed PECVD apparatus (available from SPTS, Newport, UK) in a triode electrode configuration mode in which the carrier was placed on a platform and 50 watts of 380 kHz RF energy was applied to the platform. A coil (sprinkler) is placed above the platform, and 300 watts of 13.5 MHz RF energy is applied to the coil (sprinkler). The temperature of the platform is 200 ° C, and the flow rate of the gas through the shower head is as shown in Table 16. Shown (flow rate is calculated as the standard cubic centimeter per minute - sccm). Thus, for example, the notation for Example 16b in the "Surface Modification Layer Deposition Process" column of Table 16 is as follows: In an STS multiplex PECVD apparatus, 200 cm of H2, 50 sccm of CH4 and 200 ° C at a platform temperature of 200 ° C 50sccm of C2F6 flows together through the showerhead into the chamber with a pressure of 300mTorr; 300W of 13.5MHz RF energy is applied to the showerhead; 50W of 380kHz RF energy is applied to the platform on which the carrier is placed And the deposition time is 120 seconds. The notation of the remaining instances in the surface treatment column can be interpreted in a similar manner. The surface energy is obtained by using three different test liquids (water (W), hexadecane (HD) and diiodomethane DIM in this case) and the Wu model, in mJ/m ² (millimeter). Joules per square meter) to calculate. For surface energy, the polar component (P) and the dispersed component (D), as well as the total energy (T), are shown. For these examples, the thickness of the surface modification layer is also shown in angstroms "Th(A)".

Example 16e is a piece of bare Eagle XG® glass that has been cleaned using SC1 chemistry and standard cleaning techniques. Example 16e shows that after cleaning, the surface energy of the glass is about 77 mJ/m ² .

Examples 16a through 16d show that a surface modifying layer can be deposited on the glass surface to modify its surface energy so that the surface of the glass can be tailored to suit a particular bonding application. An example of Table 16 is an example of a one-step process for deposition of a surface modifying layer having a desired surface energy and polar groups, as in the examples of Tables 6 and 7.

Example 16a shows that the surface modifying layer can be a plasma polymerized film deposited from a mixture of hydrogen and methane (hydrocarbon) gases. In these examples, the surface modifying layer is deposited on a clean glass carrier. Thus, the deposition of the surface modifying layer shown reduces the surface energy from about 77 mJ/m ² to about 49 mJ/m ² , which is within the range of surface energy on a typical polymer bonded surface.

Example 16b shows that the surface modifying layer can be a plasma polymerized film deposited from a mixture of hydrogen, methane (hydrocarbon), and a fluorine-containing gas (eg, C2F6, which is a fluorocarbon). In these examples, the surface modifying layer is deposited on a clean glass substrate. Thus, the deposition of the surface modifying layer shown reduces the surface energy from about 77 mJ/m ² to about 37 mJ/m ² , which is about the range of surface energy on a typical polymer bonding surface. The surface energy achieved in Example 16b was lower than the surface energy achieved in Example 16a, confirming that the addition of fluorine to the deposition gas reduced the surface energy achieved by otherwise similar surface modification layer deposition conditions.

Example 16c shows that the surface modifying layer can be a plasma polymerized film deposited from a mixture of hydrogen, methane (hydrocarbon), and a nitrogen containing gas (e.g., N2). In these examples, the surface modifying layer is deposited on a clean glass carrier. Thus, the deposition of the surface modifying layer shown reduces the surface energy from about 77 mJ/m ² to about 61 mJ/m ² , which is a typical polymerization that has been treated with O 2 plasma (as during cleaning of the polymer sheet). The surface of the object is in the range of surface energy. This surface energy is also within the range of suitability for joining the thin glass sheets to the carrier.

Example 16d shows that the surface modifying layer can be a plasma polymerized film deposited from a mixture of methane (hydrocarbon) and a nitrogen containing gas (eg, NH3). In these examples, the surface modifying layer is deposited on a clean glass substrate. Thus, the deposition of the surface modifying layer shown reduces the surface energy from about 77 mJ/m ² to about 57 mJ/m ² , again within the range of surface energy on a typical polymer bonded surface. Moreover, for some applications, this may be suitable for joining the carrier to a thin glass sheet.

Compared to the surface energy achieved by Example 16a, the surface energies achieved by Examples 16c and 16d confirm that nitrogen is added (by N2 or by The NH3) to deposition gas can increase the surface energy achieved by similar deposition gases in other cases.

The surface energy obtained by the surface modifying layer of Example 16b is less than 50 mJ/m ² (considered suitable for controlled bonding of the glass flakes to the glass carrier), however, this surface modifying layer is suitable for bonding the polymer surface Bonded to the glass joint surface. In addition, it should be noted that the surface energy produced by the surface modification layers of Examples 16c and 16d (formed from the polymerization of hydrocarbon (methane), optionally hydrogen-containing gas (H2) and nitrogen-containing gas (N2 or ammonia)) Greater than about 50 mJ/m ² , and thus may be suitable in some cases to join a thin glass sheet to a glass carrier.

The sheet joined to the carrier having the surface modifying layer on which the examples 16a to 16d according to Table 16 were placed was a substrate made of TEONEX® Q65 PEN (available from DuPont) and having a thickness of 200 μm.

In the example of Table 16, although the joint surface on which the surface modifying layer is disposed is glass, it is not necessary to be in this case. Alternatively, the bonding surface can be another suitable material having surface energy and properties similar to glass, such as germanium, polycrystalline germanium, single crystal germanium, ceramic, glass-ceramic, sapphire or quartz.

The plasma polymerized hydrocarbon polymer membrane can be derived from methane and hydrogen in a triode mode in STS multiplex CVD (Example 16a) and in an optional fluorocarbon (Example 16b), optional nitrogen (Example 16c) or optional ammonia. (Example 16d) Deposition in the case of addition. Surface energy as low as 37 mJ/M2 (Example 16b) and higher surface energy (about 61 mJ/m2, Example 16c) can be achieved using fluorocarbon or nitrogen addition. The surface energy between the energy level of Example 16b and the energy level of Example 16c can also be achieved (i.e., about 49 mJ/m2 as in Example 16a, and as in Example 16d). About 57 mJ/m2), thus demonstrating the ability to adjust the surface energy of the surface modifying layer based on the deposition conditions including the deposition gas.

For a relative example, the polymer film was placed on a bare glass carrier in the SC1 clean form (Example 16e). However, the polymer sheet is not sufficiently bonded to the carrier to allow the structure to be treated on the polymer sheet.

Moreover, the wet strength and the joint strength are required to be suitable for the organic-TFT treatment. The vastly different thermal expansion between the polymer film and the carrier minimizes the difference in expansion by selecting a high expansion glass and is best controlled by reducing the rate of the heating and cooling steps. The need to smooth and clean the surface of the substrate with minimal water absorption during processing can be met by spin coating and curing a thin layer suitable for the organic dielectric, both of which are planarized and produced for use Barriers to moisture and other contaminants.

The surface modification layer process is used to bond PEN (TEONEX® Q65 200 micro-thick sheet from DuPont) to the Corning® Eagle XG® glass carrier. Excellent bonding performance was found in the case of an amorphous carbon layer deposited using the following conditions: 50CH4, 200H2, 300W 13.56MHz RF applied to the showerhead, 50W 380kHz RF applied to the 200°C platform, and 2 minutes deposition time. The PEN was exposed to the UV-ozone cleaner for 5 minutes prior to bonding as it was found to improve adhesion. A Teflon applicator is used to coat the PEN. A 150 nm thick ring aliphatic epoxy layer was spin coated and cured on PEN to eliminate surface defects. An organic gate insulator (OGI) is a photo-patternable cycloaliphatic epoxy resin.

The bottom of the bottom gate contacts the array of organic thin film transistors formed by the following process. The 100 nm Al gate metal is deposited by: AJA The sputtering was carried out and patterned with Fuji 6512 resist lithography, and the gate was patterned by wet etching in an A-type Al etchant. The photoresist was removed by 3 min in a room temperature PGMEA bath followed by IPA/DI cleaning (the NMP based stripping agent was incompatible with the epoxy layer). A second epoxy gate insulator layer is spin coated onto the patterned gate and allowed to cure. 100 nm thick Ag S/D metal was sputtered and patterned with Fuji 6512 lithography and etched with a 1:1 mixture of Transene TFS:pH 10 buffer. Etching becomes a challenge because the Ag etch rate is fast, but the dissolution of the etch product is slow. The etching product was removed by spraying DI water by etching for 5 s, and repeated four to five times to obtain excellent results. The wetting of the tetrathienoacene-DPP co-polymer (PTDPPTFT4) organic semiconductor (OSC) layer becomes a challenge. OSC adhesion was promoted by HMDS treatment in a YES oven at 120 °C. The OSC polymer was dissolved in 6 parts of decalin at a concentration of 5 mg/mL: 4 parts of toluene. The OSC was applied by spin coating in a Laurel spinner using manual dispensing (20 seconds static, 500 rpm 30 seconds, 1000 rpm 60 seconds). The OSC film was soft baked on a hot plate at 90 ° C for 2 min and vacuum annealed at 120 ° C for 1 hr in a Salvis oven under vacuum to remove residual decalin. A short 5 second O2 plasma was used in Branson to improve adhesion, a third OGI layer was spin coated onto the OSC and directly photopatterned with 2.5 second exposure, 1 min rest and 1 min 150 °C post-bake. After 1 min of inactivity, the active layer pattern tray was developed in PGMEA for 1 min followed by IPA and DI cleaning. Dry etching using 30 sccm O2 10 sccm Ar 20 sccm CHF3 50 mT 200W 15s in Unaxis 790 RIE was used to pattern the active layer and expose the gate metal. The performance of the 75/75um TFT's is summarized in the table shown in Figure 18, which shows typical electricity. The gate current of the crystal is relative to the gate voltage and efficiency. The typical transistor has a 75 micron channel width and a 75 micron channel length, and is fabricated at the bottom gate bottom contact that is controllably bonded to the glass carrier PEN as described above. Thin film transistor. PEN is easily debonded by using a blade to initiate cracking and then peeling off. The polymer sheet can be successfully removed from the carrier, even after the above treatment, since there is no apparent crystal geometry between the OTFT on the polymer sheet and the OTFT on the mask used to create it. difference.

The above process of forming an array of bottom gate bottom contact organic thin film transistors was also successfully performed using a PEN sheet (TEONEX® Q65 200 micron thick sheet from DuPont) that was controllably bonded to Corning® A carrier made of Gorilla® glass (available from alkali metal, chemically tempered cover glass from Corning Incorporated, Corning, NY) and having a suitable surface modifying layer selected from the surface modifying layers described herein. .

As noted above, the polymer can itself be a substrate on which other devices are fabricated. Alternatively, the polymer can be a polymeric surface on a composite substrate such as a glass/polymer composite. In this case, the polymer surface of the glass/polymer composite will face the carrier and will be bonded thereto as described above, while the glass surface of the glass/polymer composite will be exposed to electrons or other structures that can be fabricated thereon. The surface. After fabrication of the electronic or other structure on the glass surface of the glass/polymer composite, the polymer surface of the composite can be peeled off from the surface modifying layer on the carrier. This embodiment may be advantageous because the glass layer in the glass/polymer composite becomes particularly thin, for example, having the following thicknesses: 50 microns, 40 micron, 30 microns, 20 microns, 10 microns or 5 microns. In this case, the polymer portion of the glass/polymer composite not only acts as a bonding surface for attaching the composite to the carrier, it can also impart some disposal advantages to the composite when the composite is not on the carrier.

in conclusion

It should be emphasized that the above-described embodiments of the present invention, and in particular, the preferred embodiments of the present invention are merely illustrative of the embodiments of the invention. Many variations and modifications of the above-described embodiments of the invention are possible without departing from the spirit and scope of the invention. All such modifications and variations are intended to be included within the scope of the present disclosure and the scope of the present invention, and are protected by the scope of the appended claims.

For example, while the surface modifying layer 30 of many embodiments is shown and discussed as being formed on the carrier 10, it may alternatively or additionally be formed on the sheet 20. That is, as appropriate, materials as set forth in the examples of Tables 3-12 and 16 can be applied to the carrier 10, applied to the sheet 20, applied to both the carrier 10 and the sheet 20, which will be joined together. .

Additionally, although some surface modifying layers 30 are described as controlling the joint strength to allow the sheet 20 to be removed from the carrier 10 even after the article 2 has been processed at a temperature of 400 ° C or 600 ° C, it may of course be completed better than the article 2 Objects are processed at lower temperatures of a particular test, and the ability to remove the sheet 20 from the carrier 10 without breaking the sheet 20 or carrier 10 is still achieved.

Additionally, while the controlled bonding concept has been described herein as being used for carriers and sheets, in some cases, such concepts are suitable for controlling the bonding between thicker sheets of glass, ceramic or glass ceramic, wherein It may be desirable to detach the sheets (or portions thereof) from one another.

Additionally, although the controlled bonding concept herein has been described as being applicable to glass vehicles and glass sheets, the carriers may be fabricated from other materials such as ceramics, glass ceramics or metals. Similarly, sheets that are controllably bonded to the carrier can be made from other materials, such as ceramic or glass ceramic.

In addition, although the surface modifying layers described above in Examples 3 and 5-12 are described as being formed by plasma polymerization, other techniques may be possible, for example, by thermal evaporation sputtering, in the form of gas and bonding. UV activation of the surface reacting material, or wet chemical method.

In addition, although the carbonaceous surface modifying layer formed by the plasma polymerization of Examples 6-12 is formed using methane as a polymer forming gas, other carbon source materials may be possible. For example, the carbonaceous source can include at least one of the following: 1) a hydrocarbon (alkane, alkene, alkyne, or aromatic compound). Alkanes include, but are not limited to, methane, ethane, propane, and butane; olefins include, but are not limited to, ethylene, propylene, and butene; alkynes include, but are not limited to, acetylene, methyl acetylene, ethyl acetylene, and dimethyl acetylene. ; aromatic compounds include, but are not limited to: benzene, toluene, xylene, ethylbenzene); 2) alcohols (including: methanol, ethanol, propanol); 3) aldehydes or ketones (including: formaldehyde, acetaldehyde and acetone); 4) amines (including: methylamine, dimethylamine, trimethylamine and ethylamine); 5) organic acids (including: formic acid and acetic acid); 6) nitriles (including: acetonitrile); 7) CO; and 8) CO2. Alternatively, the carbonaceous source may comprise one or more of the following: 1) a saturated or unsaturated hydrocarbon, or 2) a nitrogenous or 3) an oxygen containing saturated or unsaturated hydrocarbon, 4) CO or CO2. Some typical carbonaceous source materials include carbonaceous gases such as methane, ethane, propane, butane, ethylene, propylene, propyne, acetylene, MAPP, CO, and CO2.

In addition, although the polar groups used to treat the surface modifying layer and thereby increase the surface energy of the surface modifying layer as in Examples 5 and 8-12, or the surface modifying layer itself as in Examples 7, 16c, 16d The polar groups formed are nitrogen and oxygen, but other polar groups such as sulfur and/or phosphorus may be possible.

In addition, although N2 and NH3 are used as nitrogen-containing gas, other nitrogen-containing materials such as hydrazine, N2O, NO, N2O4, methylamine, dimethylamine, trimethylamine and ethylamine may be used. Acetonitrile.

Further, although the oxygen-containing gas used is N2-O2 and O2, other oxygen-containing gases such as O3, H2O, methanol, ethanol, propanol, N2O, NO, and N2O4 may be used.

As can be seen from the examples discussed herein, surface modifying layers including their subsequent processing surface modifying layers can be achieved from about 1 nm (Example 16b) or 2 nm (Examples 3, 4) to about 10 nm (Example 12c, 8.8 nm). thickness. In addition, thicker surface modifying layers are also possible, as explained with respect to Figure 15. However, as the thickness becomes greater than about 70 nm, the surface modifying layer begins to become translucent, which may be undesirable for applications that benefit from optical clarity.

The various concepts described above in accordance with the present application can be combined with each other in any and all different combinations. For example, various concepts can be combined according to the following aspects.

According to a first aspect, there is provided a method of controllably joining a sheet to a carrier, the method comprising: obtaining a sheet having a sheet engaging surface; obtaining a carrier having a carrier engaging surface; Depositing a surface modifying layer on at least one of the sheet joining surface and the carrier engaging surface to obtain a first surface energy on the sheet engaging surface and the carrier engaging surface; treating the surface modification a layer to vary the first surface energy to a second surface energy, wherein the second surface energy is greater than the first surface energy; and bonding the sheet bonding surface to the carrier bonding surface via the surface modifying layer.

According to a second aspect, the method of aspect 1, wherein the surface modifying layer is deposited and processed by one of: a plasma polymerization of a carbon-containing gas to form a layer, followed by treating the layer with a nitrogen-containing gas; The plasma of the carbon-containing gas is polymerized to form a layer, and then the layer is sequentially treated with a first gas followed by a second gas, wherein the first gas is one of a nitrogen-containing gas and a hydrogen-containing gas, and wherein the second gas is the a nitrogen gas and the other of the hydrogen-containing gas; a plasma of a carbon-containing gas is polymerized to form a layer, and then the layer is treated with an oxygen-containing gas; a plasma of a carbon-containing gas is polymerized to form a layer, followed by a nitrogen-containing gas and The layer is treated with oxygen gas; the plasma of the carbon-containing gas is polymerized to form a layer, and then the layer is sequentially treated with a first gas followed by a second gas, wherein the first gas is a nitrogen-containing gas and a hydrogen-containing gas, and wherein the second The gas is a nitrogen-containing gas.

According to a third aspect, the method of aspect 2, wherein the carbon-containing gas comprises at least one of a hydrocarbon, an alkane, an alkene, an alkyne or an aromatic compound.

According to a fourth aspect, the method of aspect 3, wherein the carbon-containing gas comprises at least one of methane, ethane, propane, butane, ethylene, propylene, propyne, acetylene, CO, and CO2.

According to a fifth aspect, the method of any of aspects 2-4, wherein, when a hydrogen-containing gas is used, the hydrogen-containing gas comprises H2, and wherein when the nitrogen-containing gas is used, the nitrogen-containing gas comprises ammonia At least one of N2, hydrazine, N2O, NO, N2O4, methylamine, dimethylamine, trimethylamine, ethylamine and acetonitrile.

According to a sixth aspect, the method of any of aspects 2-5, wherein when the hydrogen-containing gas is used, the hydrogen-containing gas comprises H2, and wherein when the oxygen-containing gas is used, the oxygen-containing gas comprises O2 At least one of O3, H2O, methanol, ethanol, propanol, N2O, NO, and N2O4.

According to a seventh aspect, the method of any of aspects 2-6, further comprising flowing hydrogen with the carbon-containing gas during the plasma polymerization.

According to an eighth aspect, the method of any of aspects 2, 3, and 5-7, wherein the carbon-containing gas is a fluorocarbon.

According to a ninth aspect, the method of any of aspects 2-8, wherein the surface modifying layer is deposited from a mixture of a polymer forming gas and a second gas, wherein the second gas is the total mixture 30%.

According to a tenth aspect, the method of aspect 9, wherein the second gas is hydrogen.

According to an eleventh aspect, the method of aspect 9, wherein the second gas comprises an inert gas.

According to a twelfth aspect, the method of any of aspects 1-11, wherein the sheet engaging surface comprises glass.

According to a thirteenth aspect, the method of any of aspects 1-12, wherein the carrier engaging surface comprises glass.

According to a fourteenth aspect, the method of aspect 13, wherein the at least one of the sheet joining surface and the carrier engaging surface comprises before the deposition of the surface modifying layer Average surface roughness Ra of 1 nm.

According to a fifteenth aspect, the method of aspect 13 or aspect 14, wherein at least one of the sheet bonding surface and the carrier bonding surface is deposited on the surface modifying layer and followed by O2 plasma Included after removal Average surface roughness Ra of 1 nm.

According to a sixteenth aspect, the method of aspect 13 or aspect 14, wherein the carrier engaging surface has a first average surface roughness Ra1 prior to deposition of the surface modifying layer, wherein the carrier is modified on the surface The difference between Ra1 and Ra2 after the layer has been placed thereon and subsequently removed by O2 plasma cleaning with a second surface roughness Ra2, and when the average surface roughness measurement is performed over a 5x5 micron area 1nm.

According to a seventeenth aspect, the method of any of aspects 1-16, wherein the sheet has 300 microns in thickness.

According to an eighteenth aspect, the method of any of aspects 1-17, wherein the surface modifying layer has a thickness of from 1 nm to 70 nm.

According to a nineteenth aspect, the method of any of aspects 1-17, wherein the surface modifying layer has a thickness of from 2 nm to 10 nm.

According to a twentieth aspect, the method of any of aspects 1-19, wherein the at least one of the sheet joining surface and the carrier engaging surface comprises glass, and wherein the surface modifying layer and The treatment achieves a second surface energy of from 41 mJ/m ² to 80 mJ/m ² on the joint surface.

According to Aspect A, a glass article is provided comprising: a carrier having a carrier engagement surface; a surface modifying layer disposed on the carrier engagement surface, wherein the surface modifying layer is configured to serve When the bonding surface and the glass sheet bonding surface are joined via the surface modifying layer therebetween, after subjecting the article to temperature cycling by: circulating at room temperature in the chamber at a rate of 9.2 ° C per minute Hold at 600 ° C for 10 minutes at 600 ° C and then cool to 300 ° C at 1 ° C per minute, and then remove the article from the chamber and allow the article to cool to room temperature, the carrier and sheet The material is not separated from one another when one is held and the other is subjected to gravity, there is no outgassing from the surface modifying layer during the temperature cycle, and the sheet can be separated from the carrier without the The carrier and the thinner one of the sheets are broken into two or more pieces.

According to aspect B, there is provided a glass article comprising: a carrier having a carrier engaging surface; a sheet having a sheet engaging surface; a surface modifying layer disposed on the carrier engaging surface and the sheet One of the bonding surfaces; the carrier bonding surface and the sheet bonding surface are joined via the surface modifying layer therebetween, wherein bonding the sheet to the surface energy of the carrier has the property of After the object is subjected to a temperature cycle by: Heating from room temperature to 600 ° C at a rate of 9.2 ° C per minute in the chamber, holding at 600 ° C for 10 minutes and then cooling to 300 ° C at 1 ° C per minute, and then moving the article from the chamber In addition to and cooling the article to room temperature, the carrier and the sheet are not separated from each other while one is held and the other is subjected to gravity, and there is no degassing from the surface modifying layer during the temperature cycle. And the sheet can be separated from the carrier without breaking the carrier and the thinner one of the sheets into two or more pieces.

According to the aspect C, a glass article of any of the aspects A or B is provided, wherein the surface modifying layer has a thickness of 0.1 nm to 100 nm.

According to the aspect D, a glass article of any of the aspects A or B is provided, wherein the surface modifying layer has a thickness of 0.1 nm to 10 nm.

According to the aspect E, a glass article of any of the aspects A or B is provided, wherein the surface modifying layer has a thickness of 0.1 nm to 2 nm.

Depending on any aspect of the aspect F, a glass article of any of the aspects A to E or 1-20 is provided, wherein the carrier comprises an alkali metal-free, aluminosilicate or borosilicate or Alumina borosilicate glass, each having its own Arsenic and antimony in an amount of 0.05 wt.%.

According to any aspect of the aspect G, a glass article of any of the aspects A to F or 1-20 is provided, wherein each of the carrier and the sheet has a size of 100 mm x 100 mm or more .

10‧‧‧Carriage/glass vehicle

12‧‧‧ first surface

14‧‧‧ joint surface

16‧‧‧around

20‧‧‧Sheet/thin glass/sheet

24‧‧‧ joint surface

26‧‧‧around

30‧‧‧ Surface modification layer

Claims (20)

A method of controllably joining a sheet to a carrier, the method comprising the steps of: obtaining a sheet having a sheet engaging surface; obtaining a carrier having a carrier engaging surface; depositing a surface modifying layer And at least one of the sheet bonding surface and the carrier bonding surface to obtain a first surface energy on the sheet bonding surface and the carrier bonding surface; processing the surface modifying layer to make the first A surface energy is varied to a second surface energy, wherein the second surface energy is greater than the first surface energy; and the sheet bonding surface is bonded to the carrier bonding surface via the surface modifying layer. The method of claim 1, wherein the surface modifying layer is deposited and processed by one of: a plasma of a carbon-containing gas to form a layer, followed by treating the layer with a nitrogen-containing gas; The plasma of the carbon gas is polymerized to form a layer, and then the layer is sequentially treated with a first gas followed by a second gas, wherein the first gas is one of a nitrogen-containing gas and a hydrogen-containing gas, and wherein the second gas And the other of the nitrogen-containing gas and the hydrogen-containing gas; a plasma of a carbon-containing gas is polymerized to form a layer, and then the layer is treated with an oxygen-containing gas; a plasma of a carbon-containing gas is polymerized to form a layer, and then a nitrogen-containing gas And treating the layer with an oxygen-containing gas; a plasma of a carbon-containing gas is polymerized to form a layer, and then the layer is sequentially treated with a first gas followed by a second gas, wherein the first gas is a nitrogen-containing gas and a hydrogen-containing gas And wherein the second gas is a nitrogen-containing gas. The method of claim 2, wherein the carbon-containing gas comprises at least one of a hydrocarbon, a monoalkane, a monoolefin, an alkyne or an aromatic compound. The method of claim 3, wherein the carbon-containing gas comprises at least one of methane, ethane, propane, butane, ethylene, propylene, propyne, acetylene, CO, and CO2. The method of claim 2, wherein when a hydrogen-containing gas is used, the hydrogen-containing gas comprises H2, and wherein when a nitrogen-containing gas is used, the nitrogen-containing gas comprises ammonia, N2, hydrazine, N2O, NO, At least one of N2O4, methylamine, dimethylamine, trimethylamine, ethylamine and acetonitrile. The method of claim 2, wherein when a hydrogen-containing gas is used, the hydrogen-containing gas comprises H2, and wherein when an oxygen-containing gas is used, the oxygen-containing gas comprises O2, O3, H2O, methanol, ethanol, At least one of propanol, N2O, NO, and N2O4. The method of claim 2, further comprising the step of flowing hydrogen with the carbon-containing gas during the plasma polymerization. The method of claim 2, wherein the carbon-containing gas is a fluorocarbon. The method of claim 2, wherein the surface modifying layer is deposited from a mixture of a polymer forming gas and a second gas, wherein the second gas is the total mixture 30%. The method of claim 9, wherein the second gas is hydrogen. The method of claim 9, wherein the second gas comprises an inert gas. The method of claim 1 wherein the sheet engaging surface comprises glass. The method of claim 1 wherein the carrier engagement surface comprises glass. The method of claim 13 wherein the at least one of the sheet engaging surface and the carrier engaging surface comprises prior to deposition of the surface modifying layer One of the average surface roughness Ra of 1 nm. The method of claim 14, wherein the at least one of the sheet bonding surface and the carrier bonding surface comprises after deposition of the surface modifying layer and subsequent removal by O2 plasma One of the average surface roughness Ra of 1 nm. The method of claim 13, wherein the carrier engaging surface has a first average surface roughness Ra1 prior to deposition of the surface modifying layer, wherein the carrier has a surface modifying layer disposed thereon Subsequent to the second surface roughness Ra2 after removal by O2 plasma cleaning, and the difference between Ra1 and Ra2 when the average surface roughness measurement is performed on a 5x5 micron area. 1nm. The method of claim 1, wherein the sheet has One thickness of 300 microns. The method of claim 1, wherein the surface modifying layer has a thickness of from 1 nm to 70 nm. The method of claim 1, wherein the surface modifying layer has a thickness of from 2 nm to 10 nm. The method of any of claims 1 to 19, wherein the at least one of the sheet engaging surface and the carrier engaging surface comprises glass, and further wherein the surface modifying layer and its treatment are on the joining surface A second surface energy of from 41 mJ/m ² to 80 mJ/m ^{2 is} achieved.