KR100979780B1 - Patterning of devices - Google Patents

Abstract

A method for forming an organic switching device or a partially organic switching device, the method comprising depositing a conductive layer, a semiconductor layer, an insulating layer, or a surface modification layer by solution processing and direct printing; And defining a high resolution pattern of these layers by exposing to a focused laser beam.

Description

Patterning of Devices {PATTERNING OF DEVICES}

The present invention relates to devices such as organic electronic devices and methods for forming such devices.

Recently, semiconductor-conjugated polymer thin-film transistors (TFTs) are inexpensive, integrated logic circuits on plastic substrates (C. Drury et al., APL 73, 108 (1998)) and high-resolution active matrix displays. Is drawing attention to applications in photovoltaic integrated devices and pixel transistor switches (H. Sirringhaus et al., Science 280, 1741 (1998)). High performance TFTs have been shown in test device configurations with polymer semiconductors and inorganic metal electrodes and gate dielectric layers. Up to 0.1 cm ² / Vs of charge carrier mobilities and on-off current ratios of 10 ⁶ to 10 ⁸ , which can be compared with the performance of amorphous silicon TFTs ( H. Sirringhaus et al., Advances in Solid State Physics 39, 101 (1999)).

One of the advantages of polymer semiconductors is that they provide a simple and inexpensive solution processing. However, all polymer TFT devices and integrated circuits require the ability to form lateral patterns of polymer conductors, semiconductors and insulators. Photolithography (WO 99/10939 A2), screen printing (Z. Bao et al., Chem. Mat. 9, 1299 (1977)), soft lithographic stamping (JA Rogers, Appl. Phys. Lett. 75 , 1010 (1999)), micromoulding (JA Rogers, Appl. Phys. Lett. 72, 2716 (1998)), and direct inkjet printing (H. Sirringhaus et al., UK 0009911.9) come.

Many direct printing techniques cannot provide the patterning resolution required to define the source and drain electrodes of a TFT. In order to obtain adequate drive current and switching speed, channel lengths smaller than 10 μm are required. In the case of inkjet printing, the achievable resolution is due to the accidental variations in the droplet flight direction caused by changing the jetting conditions at the nozzle and the spread of uncontrolled ink droplets on the substrate, It is limited to 20 to 50 mu m.

This resolution limit was solved by printing on pre-patterned substrates containing different areas of surface free energy (H. Sirringhaus et al., UK 0009915.0). If water-based ink droplets of the conductive polymer are printed onto a substrate containing narrow regions of repelling of the hydrophobic surface structure, the spread of ink droplets can be limited, with a channel of only 5 μm. Transistor channels of length can be determined without accidental short between the source and drain electrodes. Hydrophobic barriers can be defined in various ways, for example, by photolithography of hydrophobic polymers or by soft lithographic stamping of self-assembled monolayers.

Embodiments of the present invention relate to methods in which electroactive polymer patterns for defining transistor devices can be printed at micrometer resolution by direct laser imaging techniques. This method is based on the scanning of a laser beam array focused on a substrate. Focused light spots cause local changes in the properties of the electrically active polymer layer or surface modification template layer. Such local variations are shown herein in various ways that can be used to make high resolution patterns of electrically active polymers. In a preferred embodiment of the present invention, the laser light is an infrared wavelength and causes a local heating effect. Alternatively, the light can be a visible or ultraviolet wavelength that causes a local change in chemical structure or local activity of the molecule upon absorption of photons. Infrared light is particularly useful when it is necessary to sharpen the edge definition or to reduce the light-induced degradation of the film to be patterned. In contrast, visible or ultraviolet light is useful when high spatial resolution needs to reach diffraction limits depending on the degree of light wavelength.

CTP imaging (computer-to-plate imaging) techniques are used in the graphic arts industry to manufacture printing plates for offset printing. The printing plates are made of aluminum or polyester and coated with suitable light-sensitive layers. These plates require that hydrophilic non-image surface regions that repel ink and lipophilic image regions that attract ink must be prepared. On the printing machine, the hydrophilic regions are shrunk with an aqueous fountain solution. In a typical platesetter before printing, the plate coating is exposed using an array of laser spots. Early CTP systems used ultraviolet and visible light, but in recent years thermal imaging using arrays of infrared laser (typical wavelengths of 830 nm or 1046 nm) spots has become more prevalent. This is because thermal imaging provides better image clarity and reduces sensitivity to daylight or room light exposure. Various techniques are used to transfer the image pattern to the photosensitive coating layer. Most visible and ultraviolet based systems are based on conventional Ag halide development. Thermal imaging is based on heat-induced modifications of the chemical structure of the photopolymer allowing the development of the image in a subsequent alkaline solution bath. An example of this is Thermal Printing Plate / 830 from Kodak Polychrome Graphics. Typical sensitivity for heat plates is on the order of 100 to 150 mJ / cm ² , which changes to a substrate temperature above 650 ° C. upon exposure. Processless plates are based on ablation / vaporisation of a thin coating layer, such as a lipophilic silver layer. Untreated plates do not require subsequent chemical development, but typically require higher exposure temperatures. An example is a Mistral plate from Agfa.

A typical platesetter for direct laser imaging is individually controlled laser diodes 5, which are connected to optical fibers 25 and focused on the surface of the printing plate using a telecentric lens system 4. 5 ', 5 ") (FIG. 10 (a)). Alternatively, a spatial light modulator 24 and a cylindrical lens assembly, such as an array of liquid crystal arrays and digital mirror devices, are provided. An unfocused laser source 5 connected to a cylindrical lens assembly 4 may be used A two-dimensional spatial light modulator connected to deflector plates may be used to speed up printing. (US 6208369) Direct laser imaging is common in the manufacture of printing plates for printing on paper.

From the above description, it is clear that the direct application of thermal printing technology to the fabrication of electrically active transistor circuits is not possible. Exposure temperatures used in thermal imagers are not compatible with the fabrication of polymer transistor circuits. Most polymer materials degrade significantly when heated to temperatures higher than 250-300 ° C. Also, in the case of electrically active circuits, the layer to be patterned forms part of the circuit, and the substrate onto which the light beams are focused may already contain several layers of electrically active polymer materials deposited thereon. In contrast, the printing plate is a medium carrier that allows the ink / toner to be transferred to the final substrate, and the sacrificial layer to be patterned on the printing plate is not part of the final image by itself. As described below, these important differences require stringent temperature requirements, stability requirements and thickness requirements that make the fabrication of active electronic circuits more difficult than those of printing plates.

The invention and its preferred aspects are set forth in the appended claims.

The invention will now be described by way of example with reference to the accompanying drawings.

1 shows a schematic of direct entry of an electrically active polymer pattern with thermal induced solubility change using a light absorbing layer.

2 shows a schematic of polymer patterning by light induced solubility change without light absorbing layer.

Figure 3 shows a schematic of the patterning of the surface modification layer by light induced solubility change followed by direct printing of the electrically active polymer.

4 shows a schematic view of a printed polymer TFT device.

5 shows a schematic of the light induced desorption of the surface modification layer followed by direct printing of the electrically active polymer.

6 shows a schematic of the light promoting surface chemical reaction followed by direct printing of the electrically active polymer.

FIG. 7 shows a schematic of the light induced thickness change followed by selective deposition of self assembled monolayers and direct printing of electrically active polymers.

8 shows a schematic of the light guided transfer of a surface modification layer followed by direct printing of an electrically active polymer.

9 shows a schematic diagram of a scanning motion of a substrate under a laser beam to create a pattern.

10 shows a schematic view of an array of individual laser diodes (a) or an array of laser spots generated from a single laser source (b).

FIG. 11 shows a schematic of reel-to-reel patterning of a large flexible substrate moving under the laser spot array.

12 shows a combination of fine feature definition of surface energy patterns by thermal printing and coarse patterning by direct printing with (a) continuous lines and (b) discontinuous interconnected lines. To show.

Figure 13 shows an active matrix array of transistors with channels of high resolution clarity from a simple array of parallel surface energy barriers.

14 shows a schematic diagram of the use of a surface modification layer to provide a limit to the fabrication of small via holes by ink jet etching.

FIG. 15 shows a schematic view of the substrate arrangement by optical detection of the alignment mark a below the moving substrate and the alignment mark design allowing only absolute positioning by changing only in the x direction.

16 shows experimental data comparing laser imaging polyimide linewidths with horizontally and vertically printed linewidths for a range of focal heights. In the case of the vertical line width, all but one data point is smaller than 5 μm. The horizontal line is consistently wider by a maximum factor of 3 than the vertical line.

17 shows a microscopic image of a vertically printed laser imaging polyimide line. Vertical lines are printed with doses of 380 mJ / cm 2. The line width of the upper half of the figure is about 3.5 mu m.

18 shows a microscopic image of a horizontally printed laser imaging polyimide line. The horizontal line is printed with a dose of 380 mJ / cm 2 (imaged simultaneously with FIG. 1). The line width is about 7 mu m, which is twice the vertical line.

19 shows a microscopic image of the narrowest laser imaging polyimide line obtained. These vertical imaging lines (developed for 20 minutes at 380 mJ / cm 2) are reduced to 2 μm width.

20 shows a microscope image of a laser imaging polyimide line in the diagonal direction. Regular toothed edges (due to the laser light spot size) may be used to increase the channel width.                 

FIG. 21 shows an optical microscope image taken under crossed polarizers of semiconductor polymer (F8T2) uniaxially aligned on top of the printed and rubbing polyimide line. The area of brightness contrast is where F8T2 is arranged uniaxially along the rubbing direction of the lower polyimide line. Alignment is achieved by annealing the F8T2 film at 150 ° C. for 10 minutes.

22 shows a self-alignment process for defining the gate electrode to overlap the source-drain electrode to the minimum.

One embodiment of the invention relates to a low temperature laser imaging method, which is a method for directly patterning an electrically active polymer film 3 coated from solution as a continuous thin film on top of a substrate 1. Suitable deposition techniques for depositing thin films from solution include other types of printing such as spin coating, blade coating, extrusion coating or screen printing. An intense laser beam of wavelength lambda is focused on the sample (sample) to induce local changes in the solubility characteristics of the electrically active polymer. The change in solubility properties is preferably caused by local heating of the polymer. The light beam is preferably an infrared wavelength that causes minimal damage to the electrically active polymer. If at the time of irradiation the polymer becomes insoluble in certain solvents that are soluble in its non-irradiated form, a pattern can be produced by cleaning the polymer film in a bath of this solvent after local exposure to radiation. Only in areas where the film is exposed will a polymer material remain on the substrate. The patterns can be written by scanning the laser beam against the sample.

In order to absorb the laser light efficiently, the light absorbing layer 2 may be deposited in direct contact with the electrically active polymer (FIG. 1). The light absorption layer preferably has a strong absorption cross section for the laser wavelength used. It is preferred that it be deposited from solution but not dissolved in the solvent depositing the electrically active polymer. The light absorbing layer may be deposited before or after the electrically active polymer. The light absorption layer may consist of a binder polymer matrix or simply dye molecules mixed into the metal film. The dye molecules may also be mixed directly into the electrically active polymer by solution deposition from the dye / polymer mixture. Alternatively, the laser wavelength is chosen such that light can be absorbed directly into the electrically active polymer without the need for additional light absorbers (FIG. 2). Many polymers have strong absorption in the mid- and near-infrared spectra ranges due to vibrations in infrared active molecules and the harmonic overtones of such vibrations.

Some electrically active polymers are subjected to heat-induced transformation, which greatly changes their solubility in different solvents. An important conjugated polymer that exhibits such thermally induced changes is the conductive polymer poly (3,4-ethylenedioxythiophene) protonated with polystyrene sulfonic acid (PEDOT / PSS). The synthesis route developed by LB Groenendaal, et al., Adv. Mat. 12, 487 (2000) polymerizes ethylenedioxythiophene monomers in an aqueous solution containing polymer PSS. . The resulting polymer solution is stable over a period of several months, so that thin films of PEDOT / PSS can be easily deposited by techniques such as spin coating. However, after annealing and drying at a temperature of 150-250 ° C., the PEDOT / PSS membrane is no longer water soluble. Local heating with focused laser radiation can then be used to develop the PEDOT / PSS pattern in a bath of solvent such as water, isopropanol or acetone. Such a pattern of PEDOT / PSS can be used as an electrode for a polymer TFT device. The mechanism of changing the heat induced solubility in PEDOT / PSS, which is also accompanied by a significant and desirable improvement in the conductivity of the film, is not fully understood at present. It may be related to the phase induction phase separation between PEDOT and PSS resulting from the strong ionic interaction between positively charged PEDOT and negatively charged PSS in intimate contact with each other. In the case of PEDOT / PSS, infrared light can be absorbed directly into PEDOT because of its strong polar absorption characteristics in near- and mid-infrared (L.B. Groenendaal, et al., Adv. Mat. 12, 487 (2000)).

Several other conjugated polymers, such as semiconducting polyfuroline polymers, also exhibit solubility changes due to changes in the thermal induction of the polymer conformation in the solid state. By heating, the polymer structure can be locally changed from a high entropy disorder state to a low entropy state with more ordered crystal structure after solution coating. This can also be seen in polymers exhibiting liquid crystal states. In this more ordered state, the solubility of most solvents is reduced, and by careful selection of the developing solution the pattern can be developed by cleaning the polymer in regions where the polymer is in a crystalline state.

Other classes of polymers suitable for this patterning technique include polymer backbone chemistry due to the release of soluble leaving groups at elevated temperatures such as, for example, polyphenylenevinylene or polythienylenevinylene precursors. There are precursor polymers that undergo a heat-induced change in structure (see, for example, "Advances in Synthetic Metals" by D. Marsitzky et al., Ed. P. Bernier, S. Lefrant, G. Bidan, Elsevier (Amsterdam). p. 1-97 (1999). Typical conversion temperatures are on the order of 200-300 ° C.

Alternatively, crosslinking reactions may be used. In this case the polymer is mixed with a crosslinker which converts the membrane into an insoluble network upon local heating. One example of a suitable crosslinker is hexamethoxymethylmelamine. As an alternative to local heating, crosslinking may be induced using an ultraviolet beam.

It is important to carefully minimize the temperature and to use long wavelengths of light to prevent degradation of the electrically active polymer during exposure. Most conjugated polymers deteriorate when heated above 300 ° C, and mineral oils are susceptible to oxidation, especially during visible and ultraviolet exposure. This can be avoided by using infrared light and carefully minimizing the laser intensity and exposure time. In addition, exposure may be performed in an inert atmosphere such as a gaseous nitrogen atmosphere.

The sample is mounted on a high precision xy-conversion stage to scan a laser light spot on the sample. Alternatively, the rotatable motor drive stage may be used to scan the light beam. In addition, a degree of free conversion in the z-direction is required to adjust the focus of the laser light spot with the layer in which the light absorbing layer is generated. The laser beam can be switched on and off by a suitable light shutter. In this way the polymer pattern can be written directly to the substrate. If the mechanical stage is controlled by a computer, the pattern can be designed using a suitable software package so that it can be transferred directly to the polymer film without the need to manufacture individual masks or printing plates.

WO 99/10939 A2 describes a technique for patterning conductive polymers by exposing ultraviolet light (UV) through a photomask. The photomask includes a pattern of metallization regions that block UV light. This polymer is mixed with a crosslinking agent. Since the crosslinking reaction is induced in the region where the film is exposed to UV light, making the polymer film insoluble, the polymer in the non-exposed area can then be removed by washing. This technique differs from that proposed in the present invention in several respects. Firstly, the above technique requires individual photomasks for the TFT circuit layout as well as each layer of the TFT circuit. In the direct writing technique of the present invention, the pattern is formed by turning on / off different focus laser light spots and scanning the sample under the laser beam. The technique of the present invention is advantageous because it does not require the manufacture of the mask plate and does not require physical contact of the mask plate with the sample. Therefore, the technique of the present invention does not contaminate or wear to the particles. The method described in WO 99/10939 A2 also relies on UV light induced crosslinking reactions. According to a preferred embodiment of the method described herein, the solubility change is induced by heat irradiation / local heating by low energy infrared light. UV exposure degrades many electrically active polymers through processes such as photooxidation, while many conjugated polymers have good thermal stability at temperatures up to 150-300 ° C.

The lateral intensity profile of the laser light spot should be as narrow as possible to achieve a pattern with well defined edges. Various techniques for focusing the laser beam may be used, ranging from lens focusing to more sophisticated techniques such as transmitting the beam through a material having a pronounced nonlinear intensity dependence of the refractive index. It is possible to realize a laser light spot having a diameter d approaching the theoretical diffraction limit determined by the light wavelength. It is also important that the beam intensity fall from maximum to zero over the distance s (ie s < d), which should be as small as possible. State-of-the-art thermal laser imagers used in the graphics technology industry achieve light spot sizes of 5-10 μm. Intensity profiles are achieved that are steeper than typical Gaussian beams and attenuate from maximum intensity to zero intensity on a length scale of the order of 1 μm or less. For example Creoscitex corporation, available from (www. Creoscitex.com) square plate and spot ^TM Trendsetter system (Squarespot ™ plate- and trendsetter system) or Galileo plate, available from Agfa (www.agfa.com) setter series Etc.

Another aspect of the invention relates to a surface modification layer that is patterned by an array of UV-lasers. The substrate is coated with a UV-sensitive surface strain layer and then imaged with an array of focus UV-lasers. The substrate is then immersed in a suitable developer to form a pattern.

The modifying layer can be a UV-exposed polyimide layer (eg those used in connection with UV-photolithography for the manufacture of LCD displays. One example of UV-exposed polyimide is RN-901 from Nissan). Such UV-polyimide is well characterized, has a known optimal exposure and can also be developed in conventional UV-resist developers (Shippley MF319, etc.).

An example of a suitable UV-laser for imaging surface strain layers is a zone-plate array lithography tool designed at MIT by HISmith et al. (Journal of Vacuum Science and Technology B, Nov / Dec, 2000). Lithographic Patterning and Confocal Imaging with Zone Plates by Dario Gil, Rajesh Menon, DJ D Carter and HISmith.

Surface patterning with resolutions of around 350 nm has been shown employing an array of laser spots over a large area (~ 1 mm) in a single pass of the laser array head using a system such as ZPAL (DJD Carter, Dario Gil, Rajesh Menon, Mark). "Vacuum Science and Technology" magazine B 17 (6) by K. Mondol, HISmith and EH Anderson, "Mask Parallel Patterning with Zone-Plate-Array Lithography," published November / December 1999)

A second embodiment of the present invention is directed to a method of generating a surface free energy pattern by laser imaging capable of directly depositing an electrically active ink in a subsequent coating or printing step (FIG. 3). A continuous surface modification layer 8 is first deposited on the substrate. The layer is chosen such that its surface has a different surface energy than the bottom of the substrate. For example, the substrate may be hydrophilic, such as a glass substrate, and the surface modification layer may be a hydrophobic polymer, such as a polyimide layer. Light absorbers may also be deposited. The layer is then deformed by local heating in the same manner as described above. A possible embodiment of the present invention is a precursor polyimide layer on a glass substrate that is converted to insoluble form by local annealing at a temperature of 200-350 ° C. The pattern can then be developed by sequentially cleaning the film with a good solvent for precursor forms such as cyclopentanone. In this way a wide range of polyimides can be patterned, such as polyimide typically patterned by conventional etching, such as Merck's ZLI-2650, or optically imageable polyimides such as Pyrarin P12720 from HD Microsystems. Likewise precursor conjugated polymer layers such as precursor poly-phenylene-vinylene can be used. A particular attractive feature of both precursor polyimide and PPV is that they can also be used as an alignment layer for active semiconductor polymers in transistors (see description below).

Patterning of the surface modification layer results in surface free energy patterns of hydrophilic and hydrophobic surface regions. If the surface energy patterned substrate is then immersed in an electrically active polymer solution in a polar (or nonpolar) solvent, deposition of the electrically active polymer will only occur in the hydrophilic (or hydrophobic) surface region. Alternatively, surface free energy patterns can be used to direct the flow and location of ink droplets of the electrically active polymer deposited by direct printing, such as ink-jet printing as described in UK 0009915.0. The method can achieve higher printing resolution, which can be significantly higher than the resolution of an inkjet printer, which is limited by variable wetting conditions on the substrate and random fluctuations in the ink drop direction. Because. High-resolution printed patterns of conductive electrically active polymers made by surface free energy patterning can be used as interconnects and electrodes in printed thin film transistor circuits (H. Sirringhaus et al., Science 290, 2123 (2000)). 4 shows the completed polymer thin film transistor after depositing the semiconductor polymer layer 11 and the dielectric polymer layer 12 and printing the conductive polymer gate electrode 13 overlapping with the source-drain channel. In forming the layer structure of the TFT as shown in Fig. 4, it is necessary to carefully select the solvent in order to avoid swelling and dissolution of the underlying layers. It is known that proper structural integrity of different polymer-polymer interfaces of TFTs can be achieved by alternating polar and nonpolar solvents (H. Sirringhaus et al., UK 0009911.9).

Since the surface modification layer is in direct contact with the semiconductor layer and the conductive electrode of the TFT, it is necessary to pay close attention so that the surface modification layer does not inhibit charge injection into the device and does not contaminate the semiconductor layer. The thickness of the surface modification layer should be as thin as possible, about 100 to 500 mm 3. This method ensures conformal coating and low parasitic source-drain contact resistance of the semiconductor thin and / or other layers coated thereon. In a preferred embodiment of the invention, the surface modification layer is an electronic grade dielectric polymer, such as polyimide, that does not contain a low molecular weight impurity fraction with mobility, which is followed by the subsequent The layers do not dissolve in the solvent used for solution deposition.                 

Patterning of the surface energy pattern as described above can be accomplished in the following manner. A solution of polyimide (PI2610) containing 830 nm absorbing dye (SDA8703) in N-methyl pyrrolidone solvent was prepared. About 10% of the solids content in the solution was dye and the remaining 90% was polyimide. The glass substrates were spin-coated with the solution so that they all had various film thicknesses (after soft baking) on the order of ˜100 nm. Soft bake was performed for 10 minutes on a hot plate at 80 ° C.

Imaging was performed in a range of laser power and height (to focus the laser and out of focus). Generally, the recommended curing temperature of polyimide is 300 minutes at 300 ° C. to allow the polyimide to rise briefly (and very locally) above this temperature when scanning a highly focused laser over a substrate. .

Dose trials were performed to confirm the exact height for focusing the laser beam on the thin film to observe variations in linewidth. Images were taken at all attempted doses (corresponding to a laser total power of 5 W to 12 W (380 to 910 mJ / cm ² )), with each dose of the image being the most in the range not wider than approximately 8 μm wide. It has narrow lines and some doses have lines as narrow as 2 μm. The process may be to some extent self-limiting. This is because it needs to be heated to several hundred degrees Celsius to cure the polyimide, at which temperature the energy-absorbing dye will be bleached. Once bleached with dye, there will be no (or very small) energy to deposit in the polyimide and the curing process is complete.

After finishing the image, the pattern in the polyimide can be observed immediately (without development), since the area of the cured film becomes thinner and the color changes slightly (the latter causes the dye to bleach and the film to be exposed to air during the imaging process). Because). The imaged sample is immersed in a solvent for preparing a resin (N-methyl pyrrolidone) to develop the pattern. The development process of the PI2610 polyimide is carried out for about 20 minutes at room temperature (and polyimide with less molecular weight would be shorter time). The development process can also be self limiting (no obvious difference between the sample developed for 24 hours and the other sample developed for 30 minutes), since the whole cured film is never dissolved in the solvent. However, the partially cured film will eventually completely dissolve from the substrate and a large portion on one sample can be completely removed by development. In this case, it is necessary to limit the development time more strictly, but in general, this problem can be avoided in the case of the film cured entirely.

The horizontal and vertical lines containing the imaged pattern are 5 μm wide on a 10 μm pitch. The vertical lines were parallel to the stage motion direction during imaging and the horizontal lines were perpendicular to that direction (so one vertical line can be imaged in one pass, while the horizontal line is its length). Requires numerous passes). The obvious difference between the horizontal line width and the vertical line width is evident in all samples, where the vertical lines are consistently narrower by factor 3 than the horizontal lines (see FIGS. 16, 17 and 18).                 

Although the focusing experiment did not show a clear trend, the line width along the laser height suggested that the laser should be focused at 30 (distance, arbitrary units). However, vertical lines up to 4 μm wide appeared at low doses (450 mJ / cm ² ) and high doses (908 mJ / cm ² ). Often the horizontal lines showed more clearly the aggregation of dye from the polyimide after exposure. This is always less evident in vertically imaged lines, as can be seen in contrast to FIGS. 17 and 18.

The narrowest of the measured lines was achieved with a dose of 380 mJ / cm ² and developed for 20 minutes. The line is shown in FIG. 19 and has a width up to about 2 μm and good uniformity.

20 shows several lines imaged diagonally after development. The jagged line edges are due to the square nature of the laser spot used for imaging. This type of line can be useful for increasing the effective channel width in the TFT relative to the actual length of the polyimide line.

Ink jet printing on top of the developed panel demonstrated that the polyimide formed hydrophobic regions on the glass while limiting the electrically active printed polymer. This was accomplished by etching the developed polyimide pattern prior to printing in oxygen plasma for 1 minute in order to make the glass sufficiently hydrophilic to effectively print the aqueous polymer.                 

The quality of the surface of the laser imaged polyimide line is good enough to align the semiconductor polymer on top after mechanical rubbing on the polyimide after patterning. This showed that the polymer became a liquid crystalline phase at a temperature of 150 ° C., so that the semiconductor polymer F8T2 of FIG. 21 was aligned on top of the polyimide line subjected to laser imaging and rubbing. When the chains of the F8T2 polymer are aligned parallel to the transport direction in the TFT, the TFT mobility increases due to the alignment of the polymer.

Another embodiment of the present invention is directed to a surface modification layer 14 that may be locally removed from a substrate by local heating. This is related to the evaporation of the surface modification layer 14. However, the temperature required for deposition needs to be low enough. The surface modification layer may be a self-assembled monolayer covalently attached to the surface, such as an alkyltrichlorosilane layer or hexamethyldisilazane layer deposited on a hydrophilic glass substrate. The heating temperature is required to break the covalent bond between the molecule and the surface. Alternatively, low molecular weight non-organic molecular layers, such as α- or β-substituted dihexylquaterthiophenes or 9,9'-, which evaporate / sublime at a temperature of about 150-300 ° C. Dialkylfluoroene monomers.

In general, the process can be used to directly pattern electrically active polymers. However, it should be borne in mind that most electrically active polymers tend to degrade / decompose during evaporation or ablation.

Yet another embodiment of the present invention is directed to a method by which surface patterns can be achieved by thermally promoting surface chemistry (FIG. 6). When the substrate is immersed in a liquid or gaseous state containing molecules 15 that can thermally activate the surface chemical reaction in the upper layer of the substrate, the surface pattern is such that the chemical reaction occurs only in the areas irradiated with the laser beam. (16) can be manufactured. One example of such a process is a substrate containing a polar hydrophilic polymer as the top layer, such as a polyvinylphenol (PVP) layer or a simple substrate glass substrate. Surface polarization can be enhanced by exposure to a plasma treatment such as radiofrequency oxygen plasma (50-250 W, 13.5 MHz for 2-5 minutes). The substrate is then immersed in an atmosphere (under air or inert nitrogen) of a self-assembled monolayer (SAM) containing an anchoring group and a hydrophobic end group for surface energy relaxation. A simple closed reactor glass vessel includes a liquid reservoir of self-assembled molecules at the bottom, in contact with and a heater and a water cooled condenser in the upper layer of the vessel. The sample is placed on the sample holder in the liquid exposed to the gas phase. The back of the sample can also be cooled. The vessel has a transparent window adjacent the sample surface into which heat radiation is introduced.

In poor nucleophilic substrates such as indium tin oxide (ITO) or many polymer substrates, surface reactions with chlorosilanes or alkoxysilanes do not proceed significantly at room temperature (Koide et al., J. Am. Chem. Soc. 122 , 11266 (2000). However, typically at temperatures above 80-100 ° C., the reaction occurs rapidly, resulting in the formation of dense self-assembled monolayers on the hydrophilic sample surface within minutes. Self-assembled monolayers cause surface hydrophobicity, whereas surfaces of unheated regions remain hydrophilic. In a subsequent printing step, this surface energy pattern can be used, for example by inkjet printing, to direct the precipitation and flow of ink droplets of the electroactive polymer. Due to the low temperatures required for activation of the reaction, the present technology is particularly suitable for patterning processes, which already contain several layers of electrically active polymers whose local temperature of the substrate cannot exceed 100 to 150 ° C. This is particularly attractive for the patterning of the gate electrode in FIG. 4. Using the surface modification layer, narrow lines of conductive polymer can be inkjet printed, which minimizes overlap capacitance between the gate and the source / drain electrodes.

In the patterning of the top layers, a self-aligning process can be used, and a pattern already defined can be used to define the area of the substrate that is exposed to radiation. For example, in the patterning of the gate electrode of the TFT in FIG. 4, a light beam may be projected on the rear side of the transparent substrate in such a way that a part of the light is blocked, absorbed or significantly attenuated by at least a previously deposited source-drain electrode. Can be. In the case of infrared and conductive polymer PEDOT, PEDOT is absorbed very high in the infrared. In this case, the light deforms only the upper layer of the region between the source-drain electrodes. This process can be used for direct self alignment patterning of the gate electrode. Alternatively, the surface modification layer 44 may be patterned on a gate dielectric top layer, such as the self-assembled monolayer. This can then be self-aligned deposition of the gate electrode material, such as direct printing, to make the overlap capacitance between the source-drain and the gate electrode very small.

Other thermally active surface reactions can be used, for example, for grafting polymers onto surfaces (W.T.S. Huck et al., Langmuir 15, 6862 (1999)). In this way it is possible to locally cause the growth of the polymer layer from the surface by promoting the reaction by light absorption.

Another embodiment of the invention is directed to a method of generating a thickness profile in a surface layer by local heating (FIG. 7). Many polymers 18 produce permanent volume changes upon annealing due to changes in polymer packing (eg due to crystallization), by crosslinking, or due to desorption of volatiles. As mentioned above, a polyimide precursor film doped with a light absorbing dye film will change thickness when exposed to infrared induced thermal conversion. Any polymer loses weight and / or changes volume when annealed near its decomposition temperature. The decomposition temperature of a particular polymer system can be determined by thermogravimetric analysis (TGA). The surface thickness profile can be used to selectively change the surface energy of the polymer surface by bringing the polymer layer into contact with the flat rubber stamp 19 inkled by the self-assembled monolayer 20. This SAM pattern can be used to provide an ink confinement barrier in subsequent printing processes of electrically active polymers. The stamp should be as flat and hard as possible, and pressurization should be as low as possible to prevent sagging of the stamp. This technique is particularly suitable for defining narrow lines 2-10 μm wide, with a small thickness difference of as much as 100 microns being sufficient to prevent contact with the surface in the stamp and recessed regions.

The present technology relates to soft lithographic stamping (Xia et al., Angew. Chem. Int. Ed. 37,550 (1998)), which uses a soft PDMS rubber stamp with a surface relief pattern. Selective deposition of SAM over a flat polymer surface. One of the drawbacks of the soft lithographic stamping technique is the difficulty in achieving accurate registration of the SAM relative to the underlying pattern and the distortion of the pattern over a wide area due to the flexibility and distortion of the stamp. By the technique proposed herein in which a surface relief pattern is formed on the polymer surface facing the stamp, it is possible to overcome the problems of stamp distortion.

Another embodiment of the present invention is directed to depositing a surface modification layer 22 directly on the sample substrate 1, which is thermally separated from a separate transfer substrate 21. It may be achieved by transcription stimulated with (Fig. 8). The distance between the sample and the transfer substrate should be as short as possible to allow accurate pattern transfer. Shorter than 1 mm is preferable, and shorter than 500 micrometers is more preferable. Also in this case, a light absorbing layer can be used between the transfer substrate and the layer (s) to be transferred. An additional release layer may be used between the absorbing layer and the emitting layer that evaporates or loses adhesion when exposed to light. Although great care must be taken to prevent degradation during heat transfer for many electrically active polymers, this method can be used for direct deposition of electrically active polymer patterns. However, this method is well suited for the deposition of the surface modification layer 23 which partially changes the surface energy and provides a barrier layer for subsequent printing of the electrically active polymer 10. Suitable emissive layer materials may be organic small molecule (which may be polar or nonpolar depending on the polarity of the sample substrate) layer which is solid at room temperature and atmospheric pressure and evaporates at temperatures above 100-300 ° C. The molecules are preferably solution treatable in order to enable low cost coating on the transfer substrate. Examples of such molecules include short conjugated oligomers having flexible side chain substituents, such as α- or β-substituted dihexylquaterthiophene or 9,9'-dialkylfluorene monomers. It should be noted that in this transfer process, the sample substrate is not directly heated, which makes this process particularly well suited for low temperature plastic substrates or substrates which already contain a temperature sensitive electrically active layer.

Similar considerations apply to the patterning of the surface strain layer deposited directly on the substrate with respect to the thickness and purity of the strain layer to be transferred.

In order to obtain high charge carrier mobility, the semiconductor polymer layer of the transistor device needs to be highly aligned, which can be achieved using a self-organization mechanism. Regioregular poly-3-hexylthiophene (P3HT), and poly-9,9'-dioctylfluorene-dithiophene copolymer (poly-9'9-dioctylfluorene-co-dithiophene, Various self-organizing semiconductor polymers can be used, such as polyfluorene copolymers such as F8T2).

It is desirable for the polymer chain to be uniaxially aligned parallel to the direction of the current flow in the TFT in order to optimally exploit the rapid in-chain movement that occurs along the polymer chain. In the case of liquid crystal semiconductor polymers such as F8T2, alignment can be induced by depositing the semiconductor polymer in an ordered molecular structure, such as a mechanically rubbed or optically aligned polyamide layer (H. Sirringhaus et al., Appl. Phys. Lett. 77,406 (2000)).

Uniaxial polymer alignment can also be induced by exposure to linearly polarized light. Photoalignable polymers include polyimides, or polymers comprising cinamate or azobenzene groups (Ichimura, Chem. Rev. 2000, 1847 (2000); Schadt et al., Nature 381,212 (1996)). The light beam used for patterning can be usefully linearly polarized, which can be used to induce an ordered molecular structure of the polymer layer and simultaneously define a pattern. This technique provides a patterned and aligned surface, such as a photoalignable polyimide, which can (a) provide high printing resolution and (b) act as an alignment layer for subsequent deposition of active semiconductor polymers such as liquid crystal polymers, for example. It can be used to create an energy barrier. The technique can also be used to directly pattern and align photoalignable semiconductor polymers, such as conjugated backbone polymers comprising azobenzene groups incorporated into the side chains.

In all the above processes, the substrate 1 may be a rigid substrate such as a thick glass substrate, or a flexible substrate such as a thin glass substrate, or polyethyleneterephtalate (PET), polyethersulfone (PES). Or a plastic substrate such as polyimide (PI). For glass substrates or high temperature plastic substrates (PI), the temperature required for patterning (100-400 ° C.) is consistent with the temperature stability of the substrate. For low temperature plastic substrates, such as PET, which are warped when heated to temperatures above 150 ° C., the wavelength of the light must be chosen so that the substrate is transparent to incident radiation and most of the heat is generated in the light absorbing layer. In this way, high temperatures for patterning can be made locally without warping of the substrate.

The patterning resolution of all the above described techniques is measured by the diameter and sharpness s (FIG. 1) of the intensity profile of the laser spot. In the case of heating by infrared light, it is important to control the thermal conductivity of the different layers on the substrate as well as the substrate itself. For best high resolution patterning applications, it is important to minimize thermal conduction. It selects a suitable material with low thermal conductivity, includes low thermal conductivity and non-absorbance dedicated interlayers between the layer to be patterned and the substrate, and / or has a pulse duration of nanoseconds. It can be achieved by operating the laser in the pulse mode having. Some strong pulses at each position will in most cases be sufficient to cause the desired thermal change. The strength and number of shots will need to be optimized to achieve an optimal balance between maximum pattern clarity and minimal material damage. If thermal conduction is minimized, optimal patterning resolution can be obtained.

In the case of photopatterning by exposure to visible or ultraviolet light, the resolution is limited only by the focusing of the laser spot in many circumstances, which can in principle be focused at the wavelength λ of the light (ie , Micrometers or less).                 

Any pattern can be defined by scanning the beam onto the sample, for example by placing the sample on a high-precision two-dimensional translation stage (FIG. 9). Using a state-of-the-art conversion stage, positioning accuracy of 0.2 to 0.5 μm can be obtained. Alternatively, in the case of a flexible substrate, the substrate may be attached to a rotating drum, and a laser assembly may be installed inside or outside the drum. The laser system and sample holder are installed in a manner that minimizes vibration of the laser beam relative to the sample. The minimum line width that can be recorded is on the spot diameter d, while the minimum spacing between the two printed lines is on the order of s. Thus, using state-of-the-art thermal imaging systems produced for the graphics technology industry, the method described herein enables direct printing of practical thin film transistor circuits with line widths on the order of 5-10 μm and minimum channel lengths of 2-5 μm or less. can do.

By using a large number of laser spots in parallel, the throughput of the technique can be significantly increased (FIG. 10). The intensity profile of each spot can overlap or spatially separate the focal plane. The former is advantageous for recording even patterns over a large area. To further enhance throughput, the laser beam can be scanned, for example by deflecting the laser beam using a high speed automatic mirror. High throughput laser direct imaging techniques have been developed for printing in the graphics technology industry.

In order to achieve high throughput at low cost, similar to newspaper printing, polymer transistor circuits can be fabricated in a reel-reel process where a continuous sheet of flexible substrate is moved through a series of processing stations (FIG. 11).

Yet another embodiment of the present invention is directed to a method of printing a composite circuit pattern from a simple surface energy pattern composed of an array of one-dimensional lines.

As the substrate continuously moves below the linear array of focused light spots, a high resolution surface energy pattern including narrow section-wise parallels can be defined by one of the techniques described above (FIG. 11). In a subsequent process, low resolution coarse printing techniques such as inkjet printing can be used to directly record composite patterns of electroactive polymers, using high resolution surface energy patterns to define all important features. . This is particularly suitable where the circuit consists of an array of similar or identical devices interconnected in a complex manner.

Examples of such circuits include active matrix arrays (FIG. 13) or gate-array logic circuits. In the latter case, the same array of one-dimensional alignment features is formed in a form that is adapted to a particular logical element. Another example is a simple NOR gate, where the alignment feature 32 may have, for example, a simple U-shape. Surface energy patterns can be used to align high resolution source-drain channels and to print low resolution interconnects, via-holes and electrodes in arbitrary locations.

The method disclosed herein can be defined as the surface energy pattern can be defined by simply rotating the flexible substrate underneath the linear array of light spots at the first process station and directly printing the required pattern of the electrically active polymer at the second process station. , Very suitable for the process of reel-reel. If necessary, it may also include intermediate steps for developing the surface energy pattern in the bath (FIG. 11).

By using one-dimensional, high resolution alignment features in combination with direct printing techniques such as inkjet printing, almost any circuit can be implemented. Simple printing across the surface energy barrier (FIG. 12) by placing one or more droplets of ink directly over the barrier line to define wiring between devices located in different portions separated by one or more surface energy barriers. can do. Alternatively, the laser beam can be switched on or switched off to block the array of one-dimensional lines at certain portions, leaving room for crossing the wirings (FIG. 13). In general, one-dimensional alignment features need not be sectioned parallel. By scanning a single laser beam or by scanning an array of beams that can be deflected individually, any one-dimensional feature can be written directly onto the substrate.

In many cases, it will be necessary to align / register the printing pattern with respect to the preprinted pattern on the substrate. For example, accurate registration is required for printing the source-drain electrodes on the surface energy pattern or the printing of the gate electrode on the underlying source-drain electrode pattern. Rough alignment is achieved by simply pressing the edge of the substrate against the support attached to the printer head placement system. This mechanical alignment is mainly used for conventional offset printing.

More accurate positioning is achieved by observing the relative alignment of the substrate pattern with respect to the printer assembly, using an optical inspection station such as a high-speed high-resolution CCD camera mounted in such a way that both the print head assembly and the substrate pattern portion are shown in the same image. can do. Using suitable software to analyze the image and perform automated pattern recognition, the relative misalignment of the substrate pattern with respect to the print head can be measured. Then, by correcting the sample's x-y position and the angle to the printer axis, accurate positioning can be achieved prior to printing.

Edge detection techniques can be used to achieve faster and more efficient positioning. An edge detection technique capable of aligning a substrate with respect to an optical printing system is disclosed in EP 10181 458 A2. They rely on measuring the transmission or reflection of the focused light beam using an optical detector in scanning across a surface having two surface portions with different optical properties. The light spots have a fixed distance known from the printing position of the print head. For example, the position of the substrate edge can be automatically determined before printing from the stepped signal recorded by the detection system.

If the alignment mark is defined in the first pattern on the substrate from a material that emits fluorescence upon excitation by the focused light beam 40 or has a different optical absorption / reflectivity, then the sample is scanned under the printing head 44 and a photodetector ( When monitoring the intensity signal of FIG. 41 (FIG. 15A), the relative position of the alignment mark with respect to the printing head can be determined.

Highly accurate alignment is achieved by converting the sample in both directions of x and y into patterns designed to provide the exact positions of x and y, such as arrays of narrow bars 42 and 43 (FIG. 15 (a)). Can be achieved.

The alignment mark can also be designed in such a way that the position and orientation of the substrate relative to the print head can both be determined in a single linear scan of the sample under the print head, ie only in the x-direction. One embodiment is shown in Figure 15 (b). In this particular case, the unknown misalignment angle β of the substrate relative to the x-axis of the positioning system and the center of the light spot in the reference frame of the positioning system from the center (0,0) on the substrate The distance Δ ₀ to a certain fixed point (0, 0) 'can be determined from the measurement positions x ₁ , x ₂ , x ₃ in which the maximum signal is detected by the photodetector in the following manner.

This one-dimensional scanning detection of alignment mark position and orientation is faster than scanning in both x and y directions. This one-dimensional scanning detection is particularly suitable for cases where y-alignment is less important, for example line features that are preferentially oriented along the y direction as shown in FIG. 14.

Alternatively, if two or more light beams (and detectors) 47, 48 are used, the position and orientation of the substrate relative to the print head are first aligned in at least two non-parallel edges 46. It is determined by scanning the head across the features and then printing with the correct alignment to the substrate feature 49. When scanning two beams across the first edge (FIG. 15C), the position of the scanning direction as well as the misorientation angle can be determined. The position of the substrate perpendicular to the scanning direction is obtained from the time interval difference between the first (rising) and second (falling) edge detection measured by the two beams.

Using a flexible substrate, warpage of the substrate may occur between subsequent patterning steps due to thermal expansion or due to mechanical stress. If this distortion is greater than the maximum overlap tolerance of the most sophisticated features 45 of the circuit, a single alignment process is not sufficient, and the alignment is local, i.e., each of the devices on the substrate. This needs to be done before printing individual groups. The alignment is repeated locally during the printing process at regular intervals, depending on the degree of distortion and the required alignment accuracy.

Since the scanning detection of alignment marks is fast, it can be performed locally without significantly lowering the print process speed. Each group of devices has an alignment mark next to them, in which the light beam of the alignment system first crosses the alignment mark, detects the edge, and corrects its position accordingly, then on the substrate Oriented to initiate deposition of material at a well defined position relative to the alignment mark to provide good alignment for any high resolution feature 45. The position of the alignment marks should be such that little or no extra operation of the print head is required. That is, the scanning operation across the alignment marks should be part of the operation required when moving the print head from one group of features to the next. The proposed single scan detection for position and orientation is particularly useful for achieving fast local alignment.

On the warped substrate, scanning detection of the relative local position between the substrate feature and the print head detects the spatial warping pattern on the substrate. Local alignment need not be performed on each feature, and the number of local alignment steps depends on the degree of warpage of the substrate and the alignment tolerance required. If the distortion pattern of the substrate is reproducible from one sample to the next, the print head is determined to determine this characteristic distortion pattern on one substrate and then automatically correct for the characteristic distortion on the undefined substrates prepared in the same state. The positioning system can be fully programmed for.

Local scanning alignment can also be used in connection with multi-nozzle inkjet printing. In this case, each print head has an array of nozzles arranged in a regular array. In most drop-on-demand inkjet systems, it is not possible to change the advancing direction of ink droplets independently from each nozzle. Thus, for a given degree of substrate warpage, the dimensions of each print head must be small enough to be accurately printed within the alignment tolerances for all nozzles in the print head by the full local alignment of the print head. In large format printers, several heads can be mounted in parallel and their position relative to the substrate can be controlled individually. However, in continuous inkjet printing, electrically conducting ink droplets from different nozzles may be individually deflected in the electric field. In theory, this allows for multi-nozzle printing by the precise local alignment of each individual nozzle.

In order to form integrated TFT circuits using devices of the type described above, it is often necessary to manufacture via hole wirings between electrodes and wirings of different layers. Different methods of making such via holes include photolithography patterning (GH Gelinck et al., Appl. Phys. Lett. 77, 1487 (2000)) or serial hole punching using a mechanical stitching machine ( CJDrury et al., WO 99/10929).

Via holes can also be made by local inkjet deposition of a solvent that is good for the layer in which the via hole wiring is to be opened (H. Sirringhaus et al., UK0009917.6). In order to obtain a small sized via hole, small ink droplets are used, and the spread of the ink droplets in the ink droplets needs to be limited.

The surface modification layer 34 patterned by the techniques described above deposits inkjet printed ink drops 33 that dissolve the lower polymer layers 35, 36 to contact the lower electrode layer 37 (FIG. 13). It can be used to limit. These via holes are then filled by printing the conductive polymer 38. For this purpose, it is important that the surface modification layer does not dissolve in the solvent used for etching. If a polar solvent is used for dissolution, this can be achieved by hydrophobic self-assembled monolayers or hydrophobic polymer layers.                 

In all of the above embodiments, the PEDOT / PSS can be replaced by any conductive polymer that can be deposited from solution. Examples are polyaniline or polypyrrole. However, some of the attractive features of PEDOT / PSS are: (a) inherent low diffusion polymer dopant (PSS), (b) excellent thermal and air stability, and (c) efficient hole charge carrier injection. It is a work function of about 5.1 eV that is well matched to the ionization potential of common hole-transporting semiconductor polymers.

The processes and devices described herein are not limited to devices made of solution treated polymers. The conductive electrodes of the several TFTs and / or the wirings in the circuit or display device (see below) are inorganic, which can be deposited, for example, by printing of a colloidal suspension or by electroplating on a pre-patterned substrate. Can be formed from conductors. In devices where not all of the layers are deposited from solution, one or more PEDOT / PSS portions of the device may be replaced with an insoluble conductive material such as a vacuum deposited conductor.

For the semiconductor layer, any solution treatable conjugated polymer or oligomeric material exhibiting a suitable field mobility above 10 ⁻³ cm ² / Vs, preferably above 10 ⁻² cm ² / Vs, may be used. Suitable materials are described, for example, in HEKatz, J. Mater. Chem. 7, 369 (1997) or Z. Bao, Advanced Materials 12, 227 (2000). Other possibilities include small conjugated molecules with soluble side chains (JG Laquindanum et al., J. Am. Chem. Soc. 120, 664 (1998)), semiconductor organic-inorganic hybrid materials self-assembled from solution (CR Kagan). Et al., Science 286, 946 (1999)) or solution deposited inorganic semiconductors such as CdSe nanoparticles (BA Ridley et al., Science 286, 746 (1999)).

The electrodes can be roughly patterned by techniques other than inkjet printing. Suitable techniques include soft lithographic printing (JA Rogers et al., Appl. Phys. Lett. 75, 1010 (1999); S. Brittain et al., Physics World, May 1998, page 31), screen printing (Z. Bao et al. Chem. Mat. 9, 12999 (1997)), and photolithography patterning (WO 99/10939) or plating. Inkjet printing is considered particularly suitable for large area patterning with good alignment for flexible plastic substrates.

Preferably all layers and components of the device and circuit are deposited and patterned by solution processing and printing techniques, but one or more components, such as a semiconductor layer, are also deposited by vacuum deposition techniques and / or photo Patterned by lithography process.

Devices such as TFTs manufactured as described above may be part of a more complex circuit or device in which one or more such devices may be integrated with each other and with other devices. Examples of applications include logic circuits and active matrix circuitry for a display or memory device, or user defined gate array circuitry.

The patterning process can be used to pattern other components of the circuit, such as wires, resistors, capacitors, and the like.

The present invention is not limited to the above embodiment. Aspects of the invention include all novel and / or inventive aspects of the concepts described herein and all novel and / or inventive combinations of the features described herein.

Applicant notes that the present invention may include any feature or combination of features or generalized concepts thereof, implicitly or explicitly disclosed herein, without limiting the scope of any of the definitions described above. It was. In view of the foregoing description, it will be apparent to those skilled in the art that various modifications may be made within the scope of the present invention.

Claims (96)

A method of forming an electrical device comprising at least one patterned layer over a substrate, the method comprising: Generating a surface energy pattern on the substrate, wherein generating the surface energy pattern comprises selectively exposing the first material layer on the substrate to a light beam such that the physical properties of the first material layer are altered. Includes; And Controlling the deposition of a second layer of material using the surface energy pattern, Wherein the second material layer forms an active layer of the electrical device. The method of claim 1, And the first material layer is made of an organic material. The method according to claim 1 or 2, Selectively exposing the layer of first material over the substrate to a light beam causes the dissolution parameters of the layer of first material in the areas exposed to the light beam to be altered. The method of claim 3, Dissolution parameters of the first material layer are altered such that the material is insoluble in a solvent that was soluble prior to exposure. The method of claim 4, wherein Cleaning the first material layer to remove material of the first material layer in areas not exposed to the light beam. The method of claim 3, The change of the dissolution parameters results in at least one of phase separation of the material of the first material layer and at least one of cross-linking of the material of the first material layer. Way. The method according to claim 1 or 2, Selectively exposing the first layer of material over the substrate to a light beam causes the surface free energy of the material of the first layer of material in regions exposed to the light beam to be altered. . The method of claim 7, wherein And wherein the first layer of material is removed from the substrate in local regions after being exposed to the light beam to reveal a surface of the underlying substrate. The method of claim 7, wherein The second material layer is made of an organic material, And the second material layer is deposited from a solution in the solvent such that the deposition pattern of the second material layer is affected by regions of altered surface free energy of the first material layer. 10. The method of claim 9, The solvent in which the material of the second material layer is deposited is selected such that the material of the second material layer is not deposited within the regions of altered surface free energy of the first material layer. The method of claim 10, The solvent in which the material of the second material layer is deposited is selected such that the material of the second material layer is not deposited in regions of the first material layer where the surface free energy is not changed by the light beam. An electric device formation method. The method according to claim 1 or 2, Selectively exposing the first layer of material over the substrate to a light beam, causing the material of the first layer of material in the areas exposed to the light beam to be removed. The method of claim 12, And wherein the material of the first material layer is desorbed or evaporated or desorbed and evaporated in the areas exposed to the light beam. The method according to claim 1 or 2, The method further includes contacting the first layer of material over the substrate with a reactive medium, and selectively exposing the first layer of material over the substrate to a light beam comprises regions exposed to the light beam. And facilitate a chemical reaction between the reactive medium in the material and the material of the first material layer. The method of claim 14, And the reactive medium is included in the first layer of material. The method of claim 14, Applying the reactive medium in gaseous or liquid form to the surface of the first material layer. The method of claim 14, And wherein said chemical reaction alters at least one of solubility, surface free energy, and electrical properties of a material of said first layer of material in regions exposed to said light beam. The method according to claim 1 or 2, Selectively exposing the first layer of material over the substrate to a light beam causes a volume of the first layer of material in regions exposed to the light beam to be altered. The method according to claim 1 or 2, And the light beam is a focused light beam. The method according to claim 1 or 2, The light beam causes local heating of the first layer of material in the areas exposed to the light beam. 21. The method of claim 20, Wherein the local temperature of the substrate in the area exposed to the light beam does not exceed 350 ° C. during exposure to the light beam. 21. The method of claim 20, And wherein the local temperature of the substrate in the area exposed to the light beam does not exceed 200 ° C. during exposure to the light beam. 21. The method of claim 20, Wherein the local temperature of the substrate in the region exposed to the light beam does not exceed 120 ° C. during exposure to the light beam. The method according to claim 1 or 2, And wherein the thickness of the first material layer is less than 1 μm. The method according to claim 1 or 2, And the first layer of material forms a conductive electrode of the electrical device. The method according to claim 1 or 2, And wherein the first material layer forms a semiconductor layer of the electrical device. The method according to claim 1 or 2, And wherein the first layer of material forms a dielectric layer of the electrical device. The method according to claim 1 or 2, And wherein said first layer of material forms a surface modification layer of said electrical device. The method according to claim 1 or 2, And wherein the light beam has a width of less than 10 μm. The method according to claim 1 or 2, And said light beam has a width of less than 1 [mu] m. The method according to claim 1 or 2, And the light beam is a laser beam. The method according to claim 1 or 2, And the light beam is an infrared beam. The method according to claim 1 or 2, And the light beam is visible light. The method according to claim 1 or 2, And the light beam is ultraviolet light. The method according to claim 1 or 2, Moving the light beam across the first layer of material to perform the selective exposure and define the required pattern. The method according to claim 1 or 2, And said light beam is a polarizing beam. The method of claim 36, And the material of the first material layer is light aligned by exposing the first material layer to the light beam. The method of claim 37, Photoalignment of the material of the first material layer coincides with the patterning of the first material layer. The method of claim 37, And wherein said second material layer is comprised of an organic material and has an ordered molecular structure in contact with said photoaligned layer. 40. The method of claim 39, And wherein said second material layer is a liquid crystal conjugated polymer layer. The method according to claim 1 or 2, And the first material layer is the patterned layer of the electrical device. The method of claim 41, wherein And wherein the first layer of material is an active layer of the electrical device. delete 10. The method of claim 9, And wherein said second layer of material is said patterned layer of said electrical device. delete A method of forming an electrical device comprising at least one patterned layer over a first substrate, the method comprising: Exposing a first material layer on a second substrate to a light beam, and the exposing is performed such that the pattern of the first material layer is transferred onto the first substrate; And depositing a second material layer on the pattern of the first material layer on the first substrate, wherein depositing the second material layer comprises depositing the second material layer on the pattern of the first material. And effected by the pattern of layers. 47. The method of claim 46 wherein And the first layer of material over the second substrate is the patterned layer of the electrical device. 49. The method of claim 47, And wherein said first layer of material over said second substrate is an active layer of said electrical device. 49. The method of claim 47, And the first material layer is a surface modification layer. The method according to any one of claims 1, 2, 46 to 49, And the electrical device is an electronic switching device. The method according to any one of claims 1, 2, 46 to 49, And wherein said electrical device is a thin film transistor device. A method of forming an electrical device comprising at least one patterned layer over a substrate, the method comprising: Patterning a first layer of material over the substrate; The patterning includes exposing the first material layer to a light beam such that the physical properties of the first material layer are changed, A portion of the light beam is blocked or attenuated by a previously deposited pattern on the substrate such that only a change of the first layer of material on the substrate occurs in areas where the light beam is blocked or attenuated. Method of forming an electrical device. A method of forming an electrical device comprising at least one patterned layer over a substrate, the method comprising: Patterning a first layer of material over the substrate; The patterning includes exposing the first material layer to a light beam such that the physical properties of the first material layer are changed, The light beam is a focused light beam, and a portion of the focused light beam is blocked or attenuated by a previously patterned third layer on the substrate so that only the patterning on the substrate in areas where the light beam is blocked or attenuated A change in only the first layer of material occurs. The method of claim 52, wherein And wherein said previously patterned third layer forms source and drain electrodes of an electronic switching device. 55. The method of claim 54, And the first material layer forms a gate electrode of the electronic switching device. 55. The compound of any one of claims 52-54, And the first material layer is a surface modification layer. The method of claim 56, wherein And further depositing another material on the surface modification layer, wherein the further step of depositing another material is performed such that deposition of the another material is limited to the region where the light beam is blocked or attenuated. An electric device formation method. The method of claim 56, wherein A further step of depositing another material on the surface modification layer, wherein the further step of depositing another material is performed such that the deposition of the another material is limited to an area where the light beam is not blocked or attenuated. An electrical device forming method. As a method of defining an integrated circuit, Moving the substrate with respect to the patterned light beam, The moving of the substrate is performed such that a first one-dimensional pattern is defined on the substrate by the patterning light beam, Wherein the first one-dimensional pattern is defined as regions having different surface free energies, and is aligned with the first one-dimensional pattern to deposit a second material pattern. delete delete The method of claim 59, And wherein said second material pattern is deposited by direct printing technique. The method of claim 62, And wherein said second pattern of material is deposited by ink jet printing. The method of claim 59, And wherein said second material pattern is deposited by immersing said substrate in a solution of said second material. 65. The method of any of claims 59, 62-64, And wherein said second material pattern is more complex than said first one-dimensional pattern. As a method of defining an integrated circuit, Moving a substrate having a set of circuit features relative to a patterned light beam, wherein the moving is performed such that the circuit features are changed by the patterned light beam. The method of claim 66, Modifying the circuit features comprises removing electrical connections between the circuit features. The method of claim 66, Modifying the circuit features comprises creating electrical connections between the circuit features. The method of claim 66, Wherein the alteration of the circuit features consists of defining channels between source and drain electrodes of the array of transistor devices. The method of any one of claims 59, 62-64, 66-69, And said patterning light beam is generated by a patterning head. The method of claim 70, And the patterning head generates a plurality of light beams spaced apart in a normal direction with respect to a straight line, the method comprising exposing the substrate to the plurality of light beams. The method of any one of claims 59, 62-64, 66-69, And modulating the patterned light beam upon the movement. The method of any one of claims 59, 62-64, 66-69, And said patterning light beam is a focused beam. The method of any one of claims 59, 62-64, 66-69, And said patterning light beam is a laser beam. The method of any one of claims 59, 62-64, 66-69, And the width of the patterned light beam is less than 10 microns. The method of any one of claims 59, 62-64, 66-69, Wherein the width of the patterned light beam is less than 1 μm. A method of determining relative alignment of features and optical read head on a substrate, the method comprising: Wherein the substrate has a set of optically detectable alignment marks comprising a first straight line, a second straight line spaced parallel to the first straight line, and a third straight line spaced at a predetermined angle from the first straight line; The alignment marks have a predetermined offset from the feature, Scanning the optical read head with respect to the substrate with a straight line scanning line, and the scanning step includes a distance along the straight line scanning line between the first straight line and the second straight line and the first straight line and the third straight line. A distance along the straight scanning line between straight lines is determined to be determined; And And determining, by the determined distances and the offset, a relative position of the optical read head and the feature. 78. The method of claim 77 wherein Determining the relative position of the optical read head and the feature is a relational equation

Is performed according to α is an angle between the second straight line and the third straight line, β is an angle between the second straight line and the straight line scanning line, Δ is the distance along the first straight line between the starting point of the first straight line and the point at which the first straight line intersects the straight line scanning line, d is the vertical distance between the first straight line and the second straight line, s is a vertical distance between the second straight line and the third straight line at a point where a line perpendicular to the first straight line passes through a starting point of the first straight line, x _n and y _n are Cartesian coordinates of the point where the straight scanning line intersects the nth line, And said predetermined offset of said feature from said alignment marks is indicative of an offset of said feature from said starting point. 79. The method of claim 77 or 78, And a material processing unit integrated in the optical read head. The method of claim 79, And wherein said material processing unit is one of a deposition unit and a light beam generating unit. 79. The method of claim 77 or 78, And the feature is a linear feature. 82. The method of claim 81 wherein And wherein said feature is perpendicular to said first straight line. 79. The method of claim 77 or 78, Wherein the first straight line, the second straight line, and the third straight line are defined by at least one linear region of optical contrast change in the substrate. How to determine alignment. A method of manufacturing an electronic circuit device on a substrate comprising an array of features each having corresponding alignment marks, the method comprising: Performing a local alignment step with respect to at least two of the features in the substrate, and Each local positioning step comprises determining a relative position of each said feature relative to a material processing unit by scanning the read head in a straight line across the alignment mark corresponding to the feature. Device manufacturing method. 85. The method of claim 84, And a fixed spatial relationship exists between the material processing unit and the read head. 86. The method of claim 85, And the read head is integrated with the material processing unit. 87. The method of any one of claims 84 to 86, After each of the local alignment steps, a material deposition step comprising depositing material from the material processing unit to the substrate is performed. 87. The method of any one of claims 84 to 86, After each said local alignment step, a material processing deposition step comprising processing material on said substrate by said material processing unit is performed. 88. The method of claim 87 wherein And wherein said material is deposited or processed at a predetermined spatial offset from each said alignment mark. 87. The method of any one of claims 84 to 86, And said substrate is a flexible substrate. 87. The method of any one of claims 84 to 86, And said material processing unit is an inkjet printing head. 87. The method of any one of claims 84 to 86, The alignment marks include a first straight line, a second straight line spaced parallel to the first straight line, a third straight line spaced at a predetermined angle from the first straight line, and the alignment marks are previously separated from the feature Having a determined offset, and wherein said process of registration includes detection of a series of optical signals by said read head. The method of claim 56, wherein And the surface modification layer is a self-assembled monolayer. The method of claim 1, And wherein the second material layer is deposited from solution such that the second material layer has a deposition pattern that is affected by the surface energy pattern. 79. The method of claim 77 or 78, And said substrate is a flexible substrate. The method of claim 79, And wherein said material processing unit is an inkjet printing head.

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