WO2017024197A1 - Articles et procédés de liaison de feuilles à des supports - Google Patents

Articles et procédés de liaison de feuilles à des supports Download PDF

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Publication number
WO2017024197A1
WO2017024197A1 PCT/US2016/045694 US2016045694W WO2017024197A1 WO 2017024197 A1 WO2017024197 A1 WO 2017024197A1 US 2016045694 W US2016045694 W US 2016045694W WO 2017024197 A1 WO2017024197 A1 WO 2017024197A1
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WO
WIPO (PCT)
Prior art keywords
sheet
modification layer
bonding surface
bonding
carrier
Prior art date
Application number
PCT/US2016/045694
Other languages
English (en)
Inventor
Kaveh Adib
Robert Alan Bellman
Original Assignee
Corning Incorporated
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Corning Incorporated filed Critical Corning Incorporated
Publication of WO2017024197A1 publication Critical patent/WO2017024197A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/28—Deposition of only one other non-metal element
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08—Dimensions, e.g. volume
    • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105—Thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
    • B32B2315/08—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/0007—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving treatment or provisions in order to avoid deformation or air inclusion, e.g. to improve surface quality
    • B32B37/0015—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving treatment or provisions in order to avoid deformation or air inclusion, e.g. to improve surface quality to avoid warp or curl
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/10—Removing layers, or parts of layers, mechanically or chemically

Definitions

  • the present disclosure relates generally to articles and methods for processing sheets on carriers and, more particularly, to articles and methods for processing flexible glass sheets on glass carriers.
  • display devices can be manufactured using a glass carrier laminated to one or more thin glass substrates. It is anticipated that the low permeability and improved temperature and chemical resistance of the thin glass will enable higher performance longer lifetime flexible displays.
  • the concept involves bonding a thin sheet, for example, a flexible glass sheet, to a carrier initially by van der Waals forces, then increasing the bond strength in certain regions while retaining the ability to remove portions of the thin sheet after processing the thin sheet/carrier to form devices (for example, electronic or display devices, components of electronic or display devices, OLED materials, photo-voltaic (PV) structures, or thin film transistors (TFTs)), thereon.
  • devices for example, electronic or display devices, components of electronic or display devices, OLED materials, photo-voltaic (PV) structures, or thin film transistors (TFTs)
  • At least a portion of the thin glass is bonded to a carrier such that there is prevented device process fluids from entering between the thin sheet and carrier, whereby there is reduced the chance of contaminating downstream processes, i.e., the bonded seal portion between the thin sheet and carrier is hermetic, and in some preferred embodiments, this seal encompasses the outside of the article thereby preventing liquid or gas intrusion into or out of any region of the sealed article.
  • LTPS low temperature polysilicon
  • vacuum, and wet etch environments may be used.
  • lower temperatures are suitable.
  • temperatures in the range of from about 400°C to about 450°C are typically used, whereas for amorphous silicon (a-Si) TFT fabrication, temperatures on the order of about 350°C are typically used.
  • a-Si amorphous silicon
  • temperatures on the order of about 250°C are typically used.
  • the processing conditions for the device being made will limit the materials that may be used, and place high demands on the carrier/thin sheet.
  • a carrier approach that utilizes the existing capital infrastructure of the manufacturers, enables processing of thin glass, i.e., glass having a thickness ⁇ 0.3 millimeters (mm) thick, without contamination or loss of bond strength between the thin glass and carrier at various processing temperatures, and wherein the thin glass de-bonds easily from the carrier at the end of the process.
  • One commercial advantage is that manufacturers will be able to utilize their existing capital investment in processing equipment while gaining the advantages of the thin glass sheets for PV, OLED, liquid crystal displays (LCDs) and patterned TFT electronics, for example. Additionally, such an approach enables process flexibility, including: processes for cleaning and surface preparation of the thin glass sheet and carrier to facilitate bonding; processes for strengthening the bond between the thin sheet and carrier at the bonded area; processes for maintaining releasability of the thin sheet from the carrier at a controllably bonded (or reduced/low-strength bond) area; and processes for cutting the thin sheets to facilitate extraction from the carrier.
  • the glass surfaces are cleaned to remove all metal, organic and particulate residues, and to leave a mostly silanol terminated surface.
  • the glass surfaces are first brought into intimate contact, where van der Waals and/or Hydrogen- bonding forces pull them together. With heat and optionally pressure, the surface silanol groups can condense to form strong covalent Si--0— Si bonds across the interface, permanently fusing the glass pieces. Metal, organic and particulate residue will prevent bonding by obscuring the surface, thereby preventing the intimate contact required for bonding.
  • a high silanol surface concentration is also required to form a strong bond, as the number of bonds per unit area will be determined by the probability of two silanol species on opposing surfaces reacting to condense out water.
  • Zhuravlev has reported the average number of hydroxyls per nm 2 for well hydrated silica as 4.6 to 4.9.
  • Zhuravlev, L. T. The Surface Chemistry of Amorphous Silica, Zhuravlev Model, Colloids and Surfaces A: Physiochemical Engineering Aspects 173 (2000) 1-38.
  • a challenge of known bonding methods is the temperature requirements for various device making processes.
  • the demand for higher pixel density, high resolution, and fast refresh rates on hand held displays, notebook and desktop displays, as well as the wider use of OLED displays, is pushing panel makers from amorphous silicon TFT backplanes to oxide TFT or polysilicon TFT backplanes.
  • OLEDs are a current driven device, high mobility is desired.
  • Polysilicon TFTs also offer the advantage of integration of drivers and other components activation. Higher temperature is preferred for dopant activation, ideally at temperature over 600° C. Typically, this is the highest temperature in the pSi backplane process.
  • a thin sheet—carrier article that can withstand the rigors of TFT and flat panel display (FPD) processing, including processing at various temperatures (without outgassing that would be incompatible with the semiconductor or display making processes in which it will be used), yet allow the entire area of the thin sheet to be removed (either all at once, or in sections) from the carrier so as to allow the reuse of the carrier for processing another thin sheet.
  • FPD flat panel display
  • the present specification describes methods to control the adhesion between the carrier and thin sheet to create a temporary bond sufficiently strong to survive TFT and FPD processing (including color filter, a-Si TFT, and oxide TFT processing) but weak enough to permit debonding of the sheet from the carrier, even after processing.
  • Such controlled bonding can be utilized to create an article having a re-usable carrier, or alternately an article having patterned areas of controlled bonding and covalent bonding between a carrier and a sheet.
  • the present disclosure provides surface modification layers (including various materials and associated surface heat treatments), that may be provided on the thin sheet, the carrier, or both, to control both room- temperature van der Waals and/or hydrogen bonding, and high temperature covalent bonding, between the thin sheet and carrier.
  • the room-temperature bonding may be controlled so as to be sufficient to hold the thin sheet and carrier together during vacuum processing, wet processing, and/or ultrasonic cleaning processing.
  • the high temperature covalent bonding may be controlled so as to prevent a permanent bond between the thin sheet and carrier during device processing, as well as to maintain a sufficient bond to prevent delamination during device processing.
  • the surface modification layers may be used to create various controlled bonding areas (wherein the carrier and thin sheet remain sufficiently bonded through various processes, including vacuum processing, wet processing, and/or ultrasonic cleaning processing), together with covalent bonding regions to provide for further processing options, for example, maintaining hermeticity between the carrier and sheet even after dicing the article into smaller pieces for additional device processing.
  • a glass article comprising:
  • the modification layer may comprise organogermanium
  • the modification layer bonding surface being in contact with the first sheet bonding surface, and the second sheet bonding surface being coupled with the first sheet bonding surface with the modification layer therebetween, wherein the first sheet bonding surface is bonded with the modification layer bonding surface with a bond energy of less than 600 mJ/m 2 (milli- Joules per square meter) after holding the article at 500° C for 10 minutes in a nitrogen atmosphere.
  • the first sheet bonding surface is bonded with the modification layer bonding surface with a bond energy of less than 600 mJ/m 2 after holding the glass article at 400° C for 10 minutes in a nitrogen atmosphere.
  • the modification layer has an average thickness in the range of 5 nanometers (nm) to 10 microns ( ⁇ , or micrometers).
  • the modification layer has an average thickness in the range of 10 nm to 500 nm.
  • the first sheet is glass having a thickness of less than 300 microns.
  • the organogermanium is formed by depositing an organogermane monomer on the first sheet bonding surface.
  • a glass article of aspect 1 wherein the organogermane monomer has a formula (Ri) x Si(R 2 ) y , wherein Ri is an aryl, alkyl, alkynyl and /or alkenyl and x is 1 , 2 or 3, R 2 is hydrogen, halogen, an aryl, alkyl, alkynyl and /or alkenyl, or a combination thereof and y is 1 , 2 or 3, wherein Ri and R 2 are not oxygen.
  • Ri or R 2 is an aryl, phenyl, tolyl, xylyl, naphthyl or a combination thereof.
  • R 2 is hydrogen, methyl or a combination thereof.
  • Ri or R 2 is an aryl.
  • Ri or R 2 is a di-aryl.
  • the second aspect may be provided alone or in combination with any one or more of the examples of the second aspect discussed above.
  • the organogermanium is formed by depositing an organogermane monomer on the first sheet bonding surface and the organogermane monomer is selected from the group consisting of phenylgermane, methylphenylgermane, diphenylgermane, methlydiphenylgermane and triphenylgermane.
  • the organogermanium is formed by depositing an organogermane monomer on the first sheet bonding surface and the organogermane monomer being free of an oxygen atom.
  • the modification layer is formed by deposition of a compound selected from the group consisting of phenylgermanium, methylphenylgermanium, diphenylgermanium, methlydiphenylgermanium and triphenylgermanium.
  • the modification layer is not a monolayer.
  • the modification layer is a polymerized amorphous organogermanium.
  • the second sheet is in contact with the modification layer.
  • the first aspect may be provided alone or in combination with any one or more of the examples of the first aspect discussed above.
  • a glass article comprising:
  • a modification layer having a modification layer bonding surface, the modification layer comprising organogermanium and the modification layer not being a monolayer;
  • the modification layer bonding surface being in contact with the first sheet bonding surface, and the second sheet bonding surface being coupled with the first sheet bonding surface with the modification layer therebetween, wherein the first sheet bonding surface is bonded with the modification layer bonding surface with a bond energy within the range of 150 to 1,000 mJ/m 2 over a temperature range of 400 to 500° C where bond energy at any particular temperature in the temperature range is measured by holding the glass article at that particular temperature for 10 minutes in a nitrogen atmosphere.
  • the first sheet bonding surface is bonded with the modification layer bonding surface with a bond energy within the range of 300 to 600 mJ/m 2 over a temperature range of 400 to 500° C where bond energy at any particular temperature in the temperature range is measured by holding the glass article at that particular temperature for 10 minutes in a nitrogen atmosphere.
  • the first sheet bonding surface is bonded with the modification layer bonding surface with a bond energy within the range of 350 to 500 mJ/m 2 over a temperature range of 400 to 500° C where bond energy at any particular temperature in the temperature range is measured by holding the glass article at that particular temperature for 10 minutes in a nitrogen atmosphere.
  • the third aspect may be provided alone or in combination with any one or more of the examples of the third aspect discussed above.
  • a modification layer on a bonding surface of a second sheet by depositing an organogermane monomer on the bonding surface of the second sheet, the modification layer comprising organogermanium and the modification layer having a modification layer bonding surface;
  • the surface energy of the modification layer bonding surface is increased by exposure to nitrogen, oxygen, hydrogen, carbon dioxide gas or a combination thereof.
  • the surface energy of the modification layer bonding surface is increased to equal to or greater than 55 mJ/m 2 at less than a 60° water/air contact angle.
  • the modification layer has an average thickness in the range of 5 nm to 10 microns.
  • the first sheet is glass having a thickness of 300 microns or less and the second sheet is glass having a thickness of 200 microns or greater.
  • the modification layer is formed by deposition of a compound selected from the group consisting of phenylgermanium, methylphenylgermanium, diphenylgermanium, methlydiphenylgermanium and triphenylgermanium.
  • the modification layer is not a monolayer.
  • the modification layer is a polymerized amorphous arylgermanium.
  • the organogermane monomer having formula (Ri) x Si(R. 2 )y, wherein Ri is an aryl, alkyl, alkynyl and /or alkenyl and x is 1 , 2 or 3, R 2 is hydrogen, halogen, an aryl, alkyl, alkynyl and /or alkenyl, or a combination thereof and y is 1 , 2 or 3, wherein Ri and R 2 are not oxygen.
  • the organogermane monomer has a formula (Ri) x Si(R 2 ) y , wherein Ri is an aryl, alkyl, alkynyl and /or alkenyl and x is 1 , 2 or 3, R 2 is hydrogen, halogen, an aryl, alkyl, alkynyl and /or alkenyl, or a combination thereof and y is 1 , 2 or 3, wherein Ri and R 2 are not oxygen.
  • Ri or R2 is an aryl, phenyl, tolyl, xylyl, naphthyl or a combination thereof.
  • R 2 is hydrogen, methyl or a combination thereof.
  • Ri or R 2 is an aryl.
  • Ri or R 2 is a di-aryl.
  • the organogermane monomer is selected from the group consisting of phenylgermane, methylphenylgermane, diphenylgermane, methlydiphenylgermane and triphenylgermane.
  • the organogermane monomer is free of an oxygen atom.
  • the fifth aspect may be provided alone or in combination with any one or more of the examples of the fifth aspect discussed above.
  • the bonding surface of the first sheet is bonded with the modification layer bonding surface with a bond energy of less than 600 mJ/m 2 after holding the glass article at 500° C for 10 minutes in a nitrogen atmosphere.
  • the bonding surface of the first sheet is bonded with the modification layer bonding surface with a bond energy of less than 500 mJ/m 2 after holding the glass article at 500° C for 10 minutes in a nitrogen atmosphere.
  • the fourth aspect may be provided alone or in combination with any one or more of the examples of the fourth aspect discussed above.
  • FIG. 1 is a schematic side view of an article having carrier bonded to a thin sheet with a modification layer therebetween.
  • FIG. 2 is an exploded and partially cut-away view of the article in FIG. 1.
  • FIG. 3 is a schematic view of a testing setup to measure the outgassing from thin surface treatments.
  • FIG. 4 is a graph showing Bond Energy (in mJ/m2 on the Y axis) after holding for 10 minutes in a furnace at various processing temperatures (in °C on the X axis.
  • Ranges can be expressed herein as from “about” one particular value, and/ or to "about” another particular value. When such a range is expressed, another embodiment includes from the one particular value and/ or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about,” it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
  • a first sheet for example a thin glass sheet
  • a second sheet for example a carrier
  • the carrier is typically a display grade glass substrate. Accordingly, in some situations, it is wasteful and expensive to merely dispose of the carrier after one use. Thus, in order to reduce costs of display manufacture, it is desirable to be able to reuse the carrier to process more than one thin sheet substrate.
  • Processing temperatures may include processing at a temperature > 400° C, and may vary depending upon the type of device being made. For example, processing may include temperatures up to about 450° C as in amorphous silicon or amorphous indium gallium zinc oxide (IGZO) backplane processing, or up to about 500-550° C as in crystalline IGZO processing.
  • IGZO indium gallium zinc oxide
  • a glass article 2 has a thickness 8, and includes a first sheet 20 (e.g., thin glass sheet, for example, one having a thickness of equal to or less than about 300 microns, including but not limited to thicknesses of, for example, 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) having a thickness 28, a modification layer 30 having a thickness 38, and a second sheet 10 (e.g., a carrier) having a thickness 18.
  • a first sheet 20 e.g., thin glass sheet, for example, one having a thickness of equal to or less than about 300 microns, including but not limited to thicknesses of, for example, 10-50 microns, 50-100 microns, 100-150 microns, 150-300 microns, 300, 250, 200 190, 180,
  • the glass article 2 is arranged to allow the processing of thin sheet 20 in equipment designed for thicker sheets, for example, those on the order of greater than or equal to about 0.4 mm, for example 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, or 1.0 mm, although the thin sheet 20 itself is equal to or less than about 300 microns.
  • the thickness 8, which is the sum of thicknesses 18, 28, and 38, can be equivalent to that of the thicker sheet for which a piece of equipment, for example, equipment designed to dispose electronic device components onto substrate sheets, was designed to process.
  • thickness 18 would be selected as 400 microns, assuming that thickness 38 is negligible. That is, the modification layer 30 is not shown to scale, but rather it is greatly exaggerated for sake of illustration only. Additionally, in FIG. 2, the modification layer is shown in cut-away. The modification layer can be disposed uniformly over the bonding surface 14 when providing a reusable carrier. Typically, thickness 38 will be on the order of nanometers, for example 2 nm to 1 micron, 5 nm to 250 nm, or 20 to 100 nm, or about 30, 40, 50, 60, 70, 80 or 90 nm. The presence of a modification layer may be detected by surface chemistry analysis, for example by time-of-flight secondary ion mass spectrometry (ToF Sims).
  • ToF Sims time-of-flight secondary ion mass spectrometry
  • Carrier 10 has a first surface 12, a bonding surface 14, and a perimeter 16.
  • the carrier 10 may be of any suitable material including glass.
  • the carrier can be a non-glass material, for example, ceramic, glass-ceramic, silicon, or metal, as the surface energy and/or bonding may be controlled in a manner similar to that described below in connection with a glass carrier.
  • carrier 10 may be of any suitable composition including alumino- silicate, boro-silicate, alumino-boro-silicate, soda-lime-silicate, and may be either alkali containing or alkali-free depending upon its ultimate application.
  • Thickness 18 may be from about 0.2 to 3 mm, or greater, for example 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 upon the thickness 28, and thickness 38 when such is non- negligible, as noted above.
  • the carrier 10 may be made of one layer, as shown, or multiple layers (including multiple thin sheets) that are bonded together. Further, the carrier may be of a Gen 1 size or larger, for example, Gen 2, Gen 3, Gen 4, Gen 5, Gen 8 or larger (e.g., sheet sizes from 100 mm ⁇ 100 mm to 3 meters ⁇ 3 meters or greater).
  • the thin sheet 20 has a first surface 22, a bonding surface 24, and a perimeter 26.
  • Perimeters 16 (carrier) and 26 may be of any suitable shape, may be the same as one another, or may be different from one another. Further, the thin sheet 20 may be of any suitable material including glass, ceramic, or glass-ceramic, silicon wafer, or metal. As described above for the carrier 10, when made of glass, thin sheet 20 may be of any suitable composition, including alumino-silicate, boro-silicate, alumino-boro-silicate, soda-lime- silicate, and may be either alkali containing or alkali free depending upon its ultimate application.
  • the coefficient of thermal expansion of the thin sheet can be substantially the same as that of the carrier to reduce warping of the article during processing at elevated temperatures.
  • the thickness 28 of the thin sheet 20 is 300 microns or less, as noted above.
  • the thin sheet may be of a Gen 1 size or larger, for example, Gen 2, Gen 3, Gen 4, Gen 5, Gen 8 or larger (e.g., sheet sizes from 100 mm ⁇ 100 mm to 3 meters ⁇ 3 meters or greater).
  • the glass article 2 can have a thickness that accommodates processing with existing equipment, and likewise it can survive the environment in which the processing takes place.
  • FPD processing may include wet ultrasonic, vacuum, and processing temperatures > 400° C, for example.
  • the temperature may be > 500° C, and up to less than 600° C.
  • the bonding surface 14 should be bonded to bonding surface 24 with sufficient strength so that the first sheet 20 does not separate from second sheet 10. And this strength should be maintained throughout the processing so that sheet 20 does not separate from sheet 10 during processing. Further, to allow sheet 20 to be removed from sheet 10 (so that carrier 10 may be reused), the bonding surface 14 should not be bonded to bonding surface 24 too strongly either by the initially designed bonding force, and/or by a bonding force that results from a modification of the initially designed bonding force as may occur, for example, when the article undergoes processing at temperatures of > 400° C, about 500°C, and up to less than 600° C, for example.
  • the surface modification layer 30 may be used to control the strength of bonding between bonding surface 14 and bonding surface 24 so as to achieve both of these objectives.
  • the controlled bonding force is achieved by controlling the contributions of van der Waals (and/or hydrogen bonding) and covalent attractive energies to the total adhesion energy which is controlled by modulating the polar and non-polar surface energy components of sheet 20 and sheet 10.
  • This controlled bonding is strong enough to survive FPD processing, for instance, including temperatures > 400° C, and in some instances, processing temperatures of > 500° C, and up to less than 600° C, and remain de-bondable by application of a force sufficient to separate the sheets but not to cause significant damage to sheet 20 and/or sheet 10.
  • the force should not break either the sheet 20 or sheet 10.
  • Such de-bonding permits removal of sheet 20 and the devices fabricated thereon, and also allows for re-use of sheet 10 as a carrier, or for some other purpose.
  • the modification layer 30 is shown as a solid layer between sheet 20 and sheet 10, such need not be the case.
  • the layer 30 may have an average thickness of 0.1 nm to 1 ⁇ (e.g., 1 nm to 10 nm, 10 nm to 50 nm, 100 nm, 250 nm, 500 nm to 1 ⁇ ), and may not completely cover the entire portion of the bonding surface 14.
  • the coverage may be ⁇ 100%, from 1% to 100%, from 10% to 100%, from 20% to 90%, or from 50% to 90% of the bonding surface 14.
  • the layer 30 may be up to 50 nm thick, or in other embodiments even up to 100 nm to 250 nm thick.
  • the modification layer 30 may be considered to be disposed between sheet 10 and sheet 20 even though it may not contact one or the other of sheet 10 and sheet 20.
  • the layer modifies the ability of the bonding surface 14 to bond with bonding surface 24, thereby controlling the strength of the bond between the sheet 10 and sheet 20.
  • the material and thickness of the modification layer 30, as well as the treatment of the bonding surfaces 14, 24 prior to bonding, can be used to control the strength of the bond (energy of adhesion) between sheet 10 and sheet 20.
  • Examples of coating methods, for providing a modification layer include chemical vapor deposition (CVD) techniques, and like methods.
  • CVD techniques include CVD, low pressure CVD, atmospheric pressure CVD, Plasma Enhanced CVD (PECVD), atmospheric plasma CVD, atomic layer deposition (ALD), plasma ALD, and chemical beam epitaxy.
  • the reactive gas mixture used to produce the films may also comprise a controlled amount of a source gas (carrier gas) selected from hydrogen and inert gases (Group VIII in the periodic table) for example, He, Ar, Kr, Xe.
  • a source gas selected from hydrogen and inert gases (Group VIII in the periodic table) for example, He, Ar, Kr, Xe.
  • the source gas may comprise nitrogen.
  • the amount of source gas may be controlled by the type of gas used, or by the film deposition process conditions.
  • the surface energy of the modification layer 30 can be measured upon being deposited and/or after being further treated, for example by activation with nitrogen.
  • the surface energy of the solid surface is measured indirectly by measuring the static contact angles of three liquids - water, diiodomethane and hexadecane - individually deposited on the solid surface in air. From the contact angle values of the three liquids, a regression analysis is done to calculate the polar and dispersion energy components of the solid surface.
  • the theoretical model used to calculate the surface energy values includes the following three independent equations relating the three contact angle values of the three liquids and the dispersion and polar components of surface energies of the solid surface as well as the three test liquids
  • the energy of adhesion i.e., bond energy
  • the tests simulate in a qualitative manner the forces and effects on an adhesive bond joint at a modification layer / first sheet interface.
  • Wedge tests are commonly used for measuring bonding energy.
  • ASTM D5041 Standard Test Method for Fracture Strength in Cleavage of Adhesives in Bonded Joints
  • ASTM D3762 Standard Test Method for Adhesive-Bonded Surface Durability of Aluminum
  • a summary of the test method includes recording the temperature and relative humidity under which the testing is conducted, for example, that in a lab room.
  • the first sheet is gently pre-cracked or separated at a corner of the glass article locally to break the bond between the first sheet and the second sheet.
  • a sharp razor can be used to pre-crack the first sheet from the second sheet, for example, a GEM brand razor with a thickness of 228 ⁇ 20 microns.
  • momentary sustained pressure may be needed to fatigue the bond.
  • a flat razor having the aluminum tab removed is slowly inserted until the crack front can be observed to propagate such that the crack separation increases. The flat razor does not need to be inserted significantly to induce a crack.
  • the glass article is permitted to rest for at least 5 minutes to allow the crack to stabilize. Longer rest times may be needed for high humidity environments, for example, above 50% relative humidity.
  • the glass article with the developed crack is evaluated with a microscope to record the crack length.
  • the crack length is measured from the end separation point of the first sheet from the second sheet (i.e. furthest separation point from the tip of razor) and the closest non- tapered portion of the razor.
  • the crack length is recorded and used in the following equation to calculate bond energy.
  • ⁇ is the bond energy
  • 3 ⁇ 4 is the thickness of the blade, razor or wedge
  • Ei is the Young's modulus of the first sheet 20 (e.g., thin glass sheet)
  • t w i is the thickness of the first sheet
  • E 2 is the Young's modulus of the second sheet 10 (e.g., a glass carrier)
  • t w2 is the thickness of the second sheet 10
  • L is the crack length between the first sheet 20 and second sheet 10 upon insertion of the blade, razor or wedge as described above.
  • the bond energy is understood to behave as in silicon wafer bonding, where an initially hydrogen bonded pair of wafers are heated to convert much or all the silanol-silanol hydrogen bonds to Si ⁇ 0 ⁇ Si covalent bonds. While the initial, room temperature, hydrogen bonding produces bond energies of the order of about 100-200 mJ/m 2 which allows separation of the bonded surfaces, a fully covalently bonded wafer pair as achieved during processing at elevated temperatures (on the order of 400 to 800° C) has adhesion energy of about 2000-3000 mJ/m 2 which does not allow separation of the bonded surfaces; instead, the two wafers act as a monolith.
  • the adhesion energy would be that of the coating material, and would be very low leading to low or no adhesion between the bonding surfaces 14, 24. Accordingly, the thin sheet 20 would not be able to be processed on carrier 10.
  • the inventors have found various methods of providing a modification layer 30 leading to a bonding energy that is between these two extremes, and such that there can be produced a controlled bonding sufficient to maintain a pair of glass substrates (for example a glass carrier 10 and a thin glass sheet 20) bonded to one another through the rigors of FPD processing but also of a degree that (even after high temperature processing of, e.g. > 400° C, about 500°C, and up to less than 600° C) allows the detachment of sheet 20 from sheet 10 after processing is complete.
  • the detachment of the sheet 20 from sheet 10 can be performed by mechanical forces, and in such a manner that there is no significant damage to at least sheet 20, and preferably also so that there is no significant damage to sheet 10.
  • An appropriate bonding energy can be achieved by using select surface modifiers, i.e., modification layer 30, and/or thermal or nitrogen (or oxygen, or hydrogen, or carbon dioxide, or combinations thereof) treatment of the surfaces prior to bonding.
  • the appropriate bonding energy may be attained by the choice of chemical modifiers of either one or both of bonding surface 14 and bonding surface 24, which chemical modifiers control both the van der Waal (and/or hydrogen bonding, as these terms are used interchangeably throughout the specification) adhesion energy as well as the likely covalent bonding adhesion energy resulting from high temperature processing (e.g. , on the order of > 400° C, about 500°C, and to less than 600° C).
  • an article including a thin sheet and a carrier suitable for FPD processing, can be made by coating the first sheet 20 and or second sheet 10 with an organogermanium modification layer containing, for example, at least one of phenylgermanium, methylphenylgermanium, diphenylgermanium, methlydiphenylgermanium and triphenylgermanium or a combination thereof.
  • the modification layer 30 is not a monolayer.
  • the modification layer 30 can be a polymerized amorphous organogermanium.
  • the modification layer 30 is not a self-assembled monolayer as known in the art, but has a thickness greater than 10 nm, and for example greater than 20 nm.
  • the organogermanium layer may be formed by depositing an organogermane monomer on the receiving surface.
  • the organogermane monomer can have the formula (Ri) x Ge(R.2) y , wherein Ri can be an aryl, alkyl, alkynyl and /or alkenyl and x is 1, 2 or 3, and R2 can be hydrogen, halogen, an aryl, alkyl, alkynyl and /or alkenyl, or a combination thereof and y is 1 , 2 or 3, and wherein Ri and R2 are not oxygen.
  • Ri or R2 can be an aryl, phenyl, tolyl, xylyl, naphthyl or a combination thereof.
  • Ri or R2 is an aryl or a di- or tri-aryl.
  • the organogermane monomer can be selected from phenylgermane, methylphenylgermane, diphenylgermane, methlydiphenylgermane and triphenylgermane.
  • the organogermane monomer can be free of an oxygen atom.
  • the modification layer 30 can provide a bonding surface with a surface energy in a range of from about 55 to about 75 mJ/m 2 , as measured for one surface (including polar and dispersion components), whereby the surface produces only weak bonding.
  • the desired surface energy required for bonding may not be the surface energy of the initially deposited organogermanium modification layer.
  • the deposited layer may be further treated.
  • the organogermanium modification layers can show good thermal stability. Because of the possible low surface energy of the deposited phenylgermanium layers, surface activation may be desirable for bonding to glass.
  • Surface energy of the deposited organogermanium layers can be raised to up to 76 mJ/m 2 by exposure to N 2 , N 2 -H 2 , N 2 -0 2 , NH 3 , N 2 H 4 , HN 3 , C0 2 , H 2 and then N 2 -0 2 , or mixtures thereof, plasma exposure.
  • Table 1 shows the contact angle (for water “W”, hexadecane “HD” and diiodomethane “DIM”) and surface energy (dispersion component "D", polar component "P”, and total “T”, as measured by fitting a theoretical model developed by S. Wu (1971) to three contact angles of the three aforementioned test liquids W, HD, DIM. See. S. Wu, J.
  • DPG diphenylgermane
  • Table 1 shows whether the DPG layers were plasma treated or not, and indicates the particular plasma treatment.
  • the first line of Table 1 indicates that Sample 1 of a DPG layer was not plasma treated, and that had a W contact angle of 56.8, a HD contact angle of 7.8, a DIM contact angle of 24.2, and a total surface energy of 56.2 mJ/m 2 of which the dispersion component accounted for 35.6 mJ/m 2 and the polar component accounted for 20.6 mJ/m 2 .
  • the second line of Table 1 indicates that Sample 2 of a DPG layer was plasma treated with N2 flowing at a rate of 40 seem (N2 column), a pressure of 5 mTorr (Pr column), in an Oxford ICP380 etch tool (available from Oxford Instruments, Oxfords shire UK) at 1500 Watts of power on the coil (ICP column) and an RF power of 50 Watts on the susceptor— platen on which the substrate is placed— (RF Column), for a duration of 2 seconds (Duration column) and resultantly had a W contact angle of 35.0, a HD contact angle of 21.5, a DIM contact angle of 32.8, and a total surface energy of 65.9 mJ/m 2 of which the dispersion component accounted for 33.1 mJ/m 2 and the polar component accounted for 32.8 mJ/m 2 .
  • the susceptor was at 25°C
  • the DPG layers were initially deposited onto 0.7 mm thick glass substrates made of LotusTM XT glass available from Coming Incorporated, Corning NY, after the substrates were cleaned with SCI .
  • the initial DPG layers for all the examples in Table 1 were deposited in an Applied Materials universal CVD apparatus (P5000) by sending DPG through the bubbler (the bubbler having a temperature of 85C) at about 87 standard cubic centimeters per minute (seem) by flowing Helium (He) into the chamber at 500sccm for 55 seconds, wherein the chamber was at a pressure of 9 Torr and wherein the shower head was spaced from the susceptor by a distance of 5.3 mm (210 mils), with the shower head at 30 Watts RF (13.56 MHz), and the susceptor having a temperature of 390°C.
  • P5000 Applied Materials universal CVD apparatus
  • the modification layer achieves the desired bonding of the first sheet 20 and the second sheet 10 by having an atomic percent ratio of certain atoms, e.g., oxygen, germanium and nitrogen.
  • X-ray photoelectron spectroscopy can be used to determine the surface composition of organogermanium layers before and after plasma treatment, for example, N2 plasma surface activation. It is notable that XPS is a surface sensitive technique and the sampling depth is about several nanometers.
  • N 2 surface activation of the modification layer For example, more than 60% of the nitrogen can be introduced to the surface as an amine.
  • These polar surface groups may be responsible for plasma activation of the modification layer surface, thereby raising the surface energy of the organogermanium modification layer, e.g. , phenylgermanium, to nearly that of glass (i.e. about 74 mJ/m 2 ) and thus allowing bonding with a thin glass sheet.
  • a surface modification layer 30, together with bonding surface preparation can achieve a controlled bonding area, that is, a bonding area capable of providing a room-temperature bond between sheet 20 and sheet 10 sufficient to allow the article 2 to be processed in display making processes, for example FPD type processes (including vacuum and wet processes), and yet one that controls covalent bonding between sheet 20 and sheet 10 (even at elevated temperatures) so as to allow the sheet 20 to be removed from sheet 10 (without damage to the sheets) after high temperature processing of the article 2, for example, FPD type processing.
  • FPD type processes including vacuum and wet processes
  • covalent bonding between sheet 20 and sheet 10 even at elevated temperatures
  • LTPS and Oxide TFT processes appear to be the most stringent at this time. Thus, tests representative of steps in these processes were chosen, as these are desired applications for the article 2. Annealing at 400° C is used in oxide TFT processes, whereas crystallization and dopant activation steps over 600° C are used in LTPS processing. Accordingly, the following testing was carried out to evaluate the likelihood that a particular bonding surface preparation and modification layer 30 would allow a thin sheet 20 to remain bonded to a carrier 10 throughout FPD processing, while allowing the thin sheet 20 to be removed from the carrier 10 (without damaging the thin sheet 20 and/or the carrier 10) after such processing (including processing at temperatures > 400° C, about 500°C, and up to less than 600° C).
  • the bonding energy of the modification layers to thin glass sheets can be tested under heating conditions. For example, after surface activation, thin glass can bond very well to phenylgermanium, methylphenylgermanium, and diphenylgermanium modification layer bonding surfaces with a very high bond speed consistent with the high surface energy. And high bond speed has a manufacturing advantage of reducing the overall processing time, and/or increasing the throughput, to produce article 2. Thus, initial surface energies that promote rapid bond speeds are advantageous.
  • the bond energy of thin glass bonded with nitrogen-treated organogermanium layers can rise to about 150 to 1,000 mJ/m 2 , 300 to 600 mJ/m 2 , or 350 to 500 mJ/m 2 and remain near that value.
  • the organogermanium surface modification layers may consistently maintain a bond energy less than about 600 mJ/m 2 , 700 mJ/m 2 , 800 mJ/m 2 , 900 mJ/m 2 or 1,000 mJ/m 2 with the thin glass sheet up to 400° C, 500° C, or up to less than 600° C, e.g., upon holding the glass article at 400° C, 500° C, or up to less than 600° C for 10 minutes in an inert atmosphere.
  • Polymer adhesives used in typical wafer bonding applications are generally 10-100 microns thick and lose about 5% of their mass at or near their temperature limit.
  • mass-spectrometry evolved from thick polymer films, it is easy to quantify the amount of mass loss, or outgassing, by mass-spectrometry.
  • mass-spectrometry it is more challenging to measure the outgassing from thin surface treatments that are on the order of 10 to 100 nm thick or less, for example the plasma polymer surface modification layers described above, as well as for a thin layer of pyrolyzed silicone oil or self-assembled monolayers.
  • mass-spectrometry is not sensitive enough. There are a number of other ways to measure outgassing, however.
  • TEST #1 measuring small amounts of outgassing can be based on surface energy measurements, and will be described with reference to FIG. 3.
  • a setup as shown in FIG. 3 may be used.
  • a first substrate, or carrier, 100 having the to-be-tested modification layer thereon presents a surface 104, i.e., a modification layer corresponding in composition and thickness to the modification layer 30 to be tested.
  • a second substrate, or cover, 120 is placed so that its surface 124 is in close proximity to the surface 104 of the carrier 100, but not in contact therewith.
  • the surface 124 is an uncoated surface, i.e. , a surface of bare material from which the cover is made.
  • Spacers 140 are placed at various points between the carrier 100 and cover 120 to hold them in spaced relation from one another.
  • the spacers 140 should be thick enough to separate the cover 120 from the carrier 100 to allow a movement of material from one to the other, but thin enough so that during testing the amount of contamination from the chamber atmosphere on the surfaces 104 and 124 is minimized.
  • the surface energy of bare surface 124 is measured, as is the surface energy of the surface 104, i.e., the surface of carrier 100 having the modification layer provided thereon.
  • the surface energies, wherein total, polar, and dispersion, components, can be measured by fitting a theoretical model developed by S. Wu (1971) to three contact angles of three test liquids; water, diiodomethane and hexadecane. (Reference: S. Wu, J. Polym. Sci. C, 34, 19, 1971).
  • test article After assembly, the test article is placed into a heating chamber 160, and is heated through a time-temperature cycle. The heating is performed at atmospheric pressure and under flowing N2 gas, i.e., flowing in the direction of arrows 150 at a rate of 2 standard liters per minute.
  • changes in the surface 104 are evidenced by a change in the surface energy of surface 104.
  • a change in the surface energy of surface 104 by itself does not necessarily mean that the surface modification layer has outgassed, but does indicate a general instability of the surface modification layer material at that temperature as its character is changing due to the mechanisms noted above, for example.
  • the less the change in surface energy of surface 104 the more stable the modification layer.
  • TEST #1 for outgassing uses the change in surface energy of the cover surface 124. Specifically, if there is a change in surface energy— of surface 124— of > 10 mJ/m 2 , then outgassing may be indicated. Changes in surface energy of this magnitude are consistent with contamination which can lead to loss of film adhesion or degradation in material properties and device performance. A change in surface energy of ⁇ 5 mJ/m 2 is close to the repeatability of surface energy measurements and inhomogeneity of the surface energy. This small change is consistent with minimal outgassing.
  • the carrier 100, the cover 120, and the spacers 140 can be made of Coming® Eagle XG® glass, an alkali-free alumino-boro-silicate display-grade glass available from Corning Incorporated, Corning, NY, although such need not be the case.
  • the carrier 100 and cover 120 can be 150 mm diameter 0.63 mm thick.
  • the carrier 100 and cover 120 will be made of the same material as carrier 10 and thin sheet 20, respectively, for which an outgassing test is desired.
  • Spacers 140 can be silicon spacers 0.63 mm thick, 2 mm wide, and 8 cm long, for instance, positioned between surfaces 104 and 124, thereby forming a gap of 0.63 mm between surfaces 104 and 124.
  • the chamber 160 can be incorporated in MPT-RTP600s rapid thermal processing equipment. The temperature of the chamber can be cycled from room temperature to the test limit temperature at a rate of 9 to 10° C (e.g., 9.2° C) per minute, held at the test limit temperature for about 10 minutes, and then cooled at furnace rate to 200° C. After the chamber 160 cools to 200° C, the test article can be removed. After the test article cools to room temperature, the surface energies of each surface 104 and 124 can be measured again.
  • the total surface energy of the cover at about 25 °C can be about 75 mJ/m 2 (milli- Joules per square meter), and is the surface energy of the bare glass cover, i.e., there has been no time-temperature cycle yet run whereby there has been no deposition of outgassed material yet collected on the cover.
  • the surface energy of the cover will decrease.
  • a decrease in surface energy of the cover of more than 10 mJ/m 2 is indicative of outgassing from the surface modification material on surface 104.
  • TEST #2 measuring small amounts of outgassing can based on an assembled article, i.e., one in which a thin glass sheet is bonded to a glass carrier via a organogermanium modification layer, and uses a change in percent bubble area to determine outgassing. During heating of the glass article, bubbles formed between the carrier and the thin sheet indicate outgassing of the modification layer.
  • the outgassing under the thin sheet may be limited by strong adhesion between the thin sheet and carrier. Nonetheless, layers ⁇ 10 nm thick may still create bubbles during thermal treatment, despite their smaller absolute mass loss. And the creation of bubbles between the thin sheet and carrier may cause problems with pattern generation, photolithography processing, and/or alignment during device processing onto the thin sheet. Additionally, bubbling at the boundary of the bonded area between the thin sheet and the carrier may cause problems with process fluids from one process contaminating a downstream process. A change in % bubble area of > 5 is significant, indicative of outgassing, and is not desirable. On the other hand a change in % bubble area of ⁇ 1 is insignificant and an indication that there has been no outgassing.
  • the average bubble area of bonded thin glass in a class 1000 clean room with manual bonding is about 1 %.
  • the % bubbles in bonded carriers is a function of cleanliness of the carrier, thin glass sheet, and surface preparation. Because these initial defects act as nucleation sites for bubble growth after heat treatment, any change in bubble area upon heat treatment less than 1% is within the variability of sample preparation.
  • a commercially available desktop scanner with transparency unit (Epson Expression 10000XL Photo) can be used to make a first scan image of the area bonding the thin sheet and carrier immediately after bonding. The parts can be scanned using the standard Epson software using 508 dpi (50 micron/pixel) and 24 bit RGB.
  • the image processing software first prepares an image by stitching, as necessary, images of different sections of a sample into a single image and removing scanner artifacts (by using a calibration reference scan performed without a sample in the scanner).
  • the bonded area can then be analyzed using standard image processing techniques such as thresholding, hole filling, erosion/dilation, and blob analysis.
  • the Epson Expression 1 1000XL Photo may also be used in a similar manner. In transmission mode, bubbles in the bonding area are visible in the scanned image and a value for bubble area can be determined.
  • the bubble area is compared to the total bonding area (i.e., the total overlap area between the thin sheet and the carrier) to calculate a % area of the bubbles in the bonding area relative to the total bonding area.
  • the samples are then heat treated in a MPT-RTP600s Rapid Thermal Processing system under N2 atmosphere at test-limit temperatures of 300° C, 400° C, 500° C and up to less than 600° C, for up to 10 minutes.
  • the time-temperature cycle being used can include: inserting the article into the heating chamber at room temperature and atmospheric pressure; then heating the chamber to the test-limit temperature at a rate of 9° C per minute; holding the chamber at the test-limit temperature for 10 minutes; cooling the chamber at furnace rate to 200° C; removing the article from the chamber and allow the article to cool to room temperature; and then scan the article a second time with the optical scanner.
  • the % bubble area from the second scan can be then calculated as above and compared with the % bubble area from the first scan to determine a change in % bubble area. As noted above, a change in bubble area of > 5% is significant and an indication of outgassing.
  • a change in % bubble area was selected as the measurement criterion because of the variability in original % bubble area. That is, most surface modification layers have a bubble area of about 2% in the first scan due to handling and cleanliness after the thin sheet and carrier have been prepared and before they are bonded. However, variations may occur between materials.
  • the % bubble area being measured can also be characterized as the percent of total surface area of the modification layer bonding surface not in contact with the first sheet 20 bonding surface 24.
  • the percent of total surface area of the modification layer bonding surface not in contact with the first sheet is desirably less than 5%, less than 3%, less than 1 % and up to less than 0.5% after the glass article is subjected to a temperature cycle by heating in a chamber cycled from room temperature to 400°C, 500° C, and up to less than 600° C at a rate in the range of from about 400 to about 600° C per minute and then held at the test temperature for 10 minutes before allowing the glass article to cool to room temperature.
  • the modification layer described herein allows the first sheet to be separated from the second sheet without breaking the first sheet into two or more pieces after the glass article is subjected to the above temperature cycling and thermal testing.
  • an initial DPG surface modification layer was formed using the same conditions for depositing the initial DPG layers described in connection with the Samples of Table 1, above.
  • the DPG layer was then plasma treated first with H2 and then with N2-02, for a duration of 3 seconds to bring the surface energy thereof to a level near that of bare glass, i.e., about 75 mJ/m 2 .
  • a thin glass sheet made of Coming's Willow® glass (100 microns thick, available from Corning Incorporated, Corning NY) was then bonded to the carrier via the surface modification layer. The bond was self-propagating and had good bond speed.
  • the sample was then subject to thermal testing by holding it for 10 minutes in a chamber having a temperature of 400°C and a nitrogen atmosphere. After removing the sample from the chamber and allowing it to cool, the sample was observed to have a change in blister area consistent with minimal outgassing, and the thin glass sheet was capable of being debonded from the carrier without breaking.
  • a fourth sample was not thermally treated, but was tested for initial bond energy at room temperature.
  • the bond energy of each sample, as measured after any heat treatment, is shown in FIG. 4.
  • Each temperature— room temperature, 400°C, 500°C, and 600°C— shows multiple data points which are the resultant bond energies as measured at the four different comers of the same sample. Because the bond energies for each of the four corners of any one given sample significantly overlap, the samples as seen to have uniform characteristics over their surface areas.
  • Each of the samples cycled to 400°C and 500°C was observed to have a change in blister area consistent with minimal outgassing, and was capable of having the thin glass sheet debonded from the carrier without breaking.
  • the sample cycled to 600°C was not capable of having the thin glass sheet debonded from the carrier without breaking.
  • the surface modification layers are useful to hold a thin glass sheet to a glass carrier at processing temperatures up to less than 600°C, for example 500°C, 400°C, and lower.
  • Such temperature capability makes the surface modification layers herein useful for processing color filters, a-Si TFT back planes of display devices, and/or oxide TFT back planes of display devices.
  • the surface modification layer was described as being initially deposited onto the sheet 10 (for example a carrier), such need not be the case. Instead, or in addition, the surface modification layer may be disposed on sheet 20 (for example a thin sheet).
  • the surface modification layer was described as being one layer, it may be comprised of any suitable number of layers, for example, two, three, four, or five.
  • the layer in contact with the bonding surface of sheet 10 (for example a carrier) need not be the same composition as the layer in contact with the bonding surface of the sheet 20 (for example a thin sheet).

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Abstract

L'invention concerne des couches de modification d'organogermanium ainsi que des procédés de dépôt et des traitements sous gaz inerte associés qui peuvent être appliqués à une feuille, à un support, ou aux deux, pour commander une liaison de van der Waals, par pont hydrogène et covalente, entre une feuille et un support. Les couches de modification lient la feuille et le support l'un à l'autre de telle sorte qu'une liaison permanente est évitée lors d'un traitement à haute température, de même qu'une liaison suffisante est maintenue pour éviter une déstratification pendant le traitement à haute température.
PCT/US2016/045694 2015-08-05 2016-08-05 Articles et procédés de liaison de feuilles à des supports WO2017024197A1 (fr)

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CN107635769B (zh) 2015-05-19 2020-09-15 康宁股份有限公司 使片材与载体粘结的制品和方法
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US11999135B2 (en) 2017-08-18 2024-06-04 Corning Incorporated Temporary bonding using polycationic polymers
JP7431160B2 (ja) * 2017-12-15 2024-02-14 コーニング インコーポレイテッド 基板を処理するための方法および結合されたシートを含む物品を製造するための方法

Citations (5)

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US4668574A (en) * 1983-05-03 1987-05-26 Advanced Glass Systems, Corp. Laminated safety glass
US5135808A (en) * 1990-09-27 1992-08-04 Diamonex, Incorporated Abrasion wear resistant coated substrate product
US5401305A (en) * 1991-12-26 1995-03-28 Elf Atochem North America, Inc. Coating composition for glass
US20090047506A1 (en) * 2007-08-17 2009-02-19 Shenzhen Futaihong Precision Industry Co., Ltd. Laminated glass and electronic device using same for display screen thereof
WO2014015840A1 (fr) * 2012-07-27 2014-01-30 Schott Glass Technologies (Suzhou) Co., Ltd. Verre feuilleté pour dispositif électronique mobile

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Publication number Priority date Publication date Assignee Title
US4668574A (en) * 1983-05-03 1987-05-26 Advanced Glass Systems, Corp. Laminated safety glass
US5135808A (en) * 1990-09-27 1992-08-04 Diamonex, Incorporated Abrasion wear resistant coated substrate product
US5401305A (en) * 1991-12-26 1995-03-28 Elf Atochem North America, Inc. Coating composition for glass
US20090047506A1 (en) * 2007-08-17 2009-02-19 Shenzhen Futaihong Precision Industry Co., Ltd. Laminated glass and electronic device using same for display screen thereof
WO2014015840A1 (fr) * 2012-07-27 2014-01-30 Schott Glass Technologies (Suzhou) Co., Ltd. Verre feuilleté pour dispositif électronique mobile

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