JP2013191553A - Donor substrate for transfer and process of manufacturing device substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a donor substrate for transfer and a process of manufacturing a device substrate, for providing a device of high performance by improving linearity and smoothness of a partition pattern and also having excellent durability.SOLUTION: The donor substrate for transfer includes a support body 31, a photo-thermal conversion layer 33 that absorbs light and generates heat, and a partition pattern 34 that partitions a transfer layer 37, wherein the partition pattern 34 is formed of a siloxane compound including a siloxane polymer formed by reacting at least one kind of siloxane compound.

Description

  The present invention relates to a donor substrate for transfer used for patterning a device including an organic EL element and a method for manufacturing the device substrate.

  An organic EL device is a light emitting device with an organic light emitting material sandwiched between a cathode and an anode, and emits energy generated by recombination of electrons injected from the cathode and holes injected from the anode in the organic layer. It is an element to which the principle of taking it out as energy is applied.

  Currently, a method for producing an organic layer included in an organic device typified by an organic EL element is generally formed by a dry process such as vacuum deposition, and a shadow mask or the like is used for patterning a pixel. However, such a method has problems such as low material utilization efficiency and difficulty in manufacturing a large area device.

  On the other hand, wet processes such as a photolithographic method, an inkjet method, and a printing method capable of reducing the cost and increasing the area are also being studied. However, in devices with a multilayer structure of organic thin films such as organic EL elements, there is a concern that the underlayer may change in film quality when an upper layer is applied, and it is difficult to control film thickness uniformity, etc. There is a problem that the performance decreases.

  Accordingly, a method has been developed in which a material is first prepared on a donor substrate and then transferred to a device substrate. For example, a method of manufacturing a device using a donor substrate in which a rigid support substrate is processed by etching or sandblasting to form a partition pattern is disclosed (for example, see Patent Document 1). Further, a method for manufacturing a donor substrate is disclosed in which a resin layer having heat resistance such as polyimide is formed on a donor substrate having a photothermal conversion layer formed on the entire surface, and patterning is performed by a photolithography method to form a partition pattern (for example, Patent Documents 2 and 3).

JP 2009-146715 A JP 2009-187810 A International Publication No. 2012/008443

  However, when the partition pattern is formed by etching or sandblasting disclosed in Patent Document 1, since the linearity and smoothness of the partition pattern are poor, when the solution containing the transfer material is applied in the partition pattern, There is a problem that the transfer material tends to gather on the unevenness and a uniform coating film cannot be formed.

  Moreover, the polyimide resin which is the material of the partition pattern described in Patent Documents 2 and 3 has a problem that the adhesion with the metal material which is the material of the photothermal conversion layer is poor and the durability is low.

  The present invention has been made in view of the above, and can improve a linearity and smoothness of a partition pattern, and can provide a device having excellent durability and high performance. An object is to provide a method for manufacturing a substrate.

  In order to solve the above-described problems and achieve the object, the transfer donor substrate of the present invention includes a support, a light-to-heat conversion layer that absorbs light and generates heat, a partition pattern that partitions the transfer layer, The partition pattern is formed from a siloxane composition containing a siloxane polymer (A) obtained by reacting at least one siloxane compound represented by the following general formula (1). It is characterized by.

(In General Formula (1), R ¹ is hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 16 carbon atoms, and R ² is hydrogen or carbon. An alkyl group having 1 to 10 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms, n is an integer of 0 to ^{3. When a} plurality of R ¹ and R ² are present, May be the same or different.)

  The transfer donor substrate of the present invention is characterized in that, in the above invention, the surface of the photothermal conversion layer is a rough surface.

  The donor substrate for transfer according to the present invention is characterized in that, in the above invention, the arithmetic average roughness of the surface of the photothermal conversion layer is 30 nm or more.

  The donor substrate for transfer of the present invention is characterized in that, in the above invention, the arithmetic average roughness of the surface of the support on the side where the photothermal conversion layer is formed is 30 nm or more.

  In the transfer donor substrate of the present invention, in the above invention, the photothermal conversion layer is formed on the support, and a barrier layer is formed on the surface of the partition pattern formed on the upper surface of the photothermal conversion layer. Features.

  The transfer donor substrate of the present invention is characterized in that, in the above invention, the transfer donor substrate further comprises a liquid repellent treatment layer formed on the upper surface of the partition pattern in contact with the insulating layer of the device substrate at least during transfer.

Moreover, the donor substrate for transfer of the present invention is the above-mentioned invention, wherein the siloxane polymer (A) is a photosensitive polymer having a phenolic hydroxyl group content of 0.2 mol or less with respect to 1 mol of Si atoms, The siloxane composition is a naphthoquinonediazide sulfonic acid ester of a compound having a phenolic hydroxyl group in addition to the siloxane polymer (A), wherein the ortho position and the para position of the phenolic hydroxyl group are each independently hydrogen or It includes a quinonediazide compound (B) having a substituent represented by the general formula (2), a compound having an alcoholic hydroxyl group and / or a cyclic compound (C) having a carbonyl group.
(In General Formula (2), R ³ , R ⁴ , and R ⁵ are each independently an alkyl group having 1 to 10 carbon atoms, a carboxyl group, or an optionally substituted phenyl group. , R ³ , R ⁴ and R ⁵ may combine to form a ring.)

  A device substrate manufacturing method according to the present invention includes a positioning step in which the partition pattern provided in the transfer donor substrate according to any one of the above and an insulating layer of the device substrate are aligned to face each other, And a transfer step of irradiating the photothermal conversion layer of the transfer donor substrate with light to transfer the transfer layer to the device substrate.

  The transfer donor substrate and the device substrate manufacturing method of the present invention can form a partition pattern having high adhesion to the photothermal conversion layer and excellent in linearity and smoothness, thereby improving the durability of the transfer donor substrate. A device substrate with high device performance can be provided.

FIG. 1 is a cross-sectional view showing an example of a donor substrate according to Embodiment 1 of the present invention. FIG. 2 is a cross-sectional view showing another example of the donor substrate according to Embodiment 1 of the present invention. FIG. 3 is a cross-sectional view for explaining the formation of the transfer material in the first embodiment of the present invention. FIG. 4 is a cross-sectional view showing another example of the donor substrate used in Embodiment 1 of the present invention. FIG. 5 is an enlarged photograph from the section pattern side according to the first embodiment of the present invention. FIG. 6 is a cross-sectional view showing another example of the donor substrate used in Embodiment 1 of the present invention. FIG. 7 is a cross-sectional view showing an example of a donor substrate having a liquid repellent treatment layer according to Embodiment 1 of the present invention. FIG. 8 is a cross-sectional view showing an example of the patterning method according to Embodiment 1 of the present invention. FIG. 9 is a cross-sectional view showing an example of the light emitting layer patterning method for the organic EL element in the first embodiment of the present invention. FIG. 10 is a plan view showing an example of the light irradiation method in FIG. FIG. 11 is a perspective view showing another example of the light irradiation method according to Embodiment 1 of the present invention. FIG. 12 is a perspective view showing another example of the light irradiation method according to Embodiment 1 of the present invention. FIG. 13 is a perspective view showing another example of the light irradiation method according to Embodiment 1 of the present invention. FIG. 14 is a perspective view showing another example of the light irradiation method according to Embodiment 1 of the present invention. FIG. 15: is sectional drawing which shows an example of the donor substrate concerning Embodiment 2 of this invention. FIG. 16: is sectional drawing which shows an example of the donor substrate concerning the modification 1 of Embodiment 2 of this invention. FIG. 17: is sectional drawing which shows an example of the donor substrate concerning the modification 2 of Embodiment 2 of this invention.

  Hereinafter, a method for manufacturing a transfer donor substrate and a device substrate according to the present embodiment will be described in detail with reference to the drawings. Note that the present invention is not limited to the embodiments.

(Embodiment 1)
FIG. 1 shows an example of the configuration of the donor substrate according to the first embodiment of the present invention. The donor substrate 30 includes a support 31, a photothermal conversion layer 33, a partition pattern 34, and a transfer layer 37.

  In the donor substrate 30 according to the first exemplary embodiment, the support 31 is not particularly limited as long as it has a low light absorption rate and can stably form the photothermal conversion layer 33 and the transfer layer 37 thereon. It is also possible to use a resin film. Specific resin materials include polyester, polyethylene, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyacryl, polysulfone, polyethersulfone, polyphenylene sulfide, polyimide, polyamide, polybenzoxazole, polyepoxy, polypropylene, polyolefin, and aramid. Resin, silicone resin, etc. can be used.

  As a preferable support in terms of chemical / thermal stability, dimensional stability, mechanical strength, and transparency, a glass plate can be exemplified. It can be appropriately selected from soda lime glass, alkali-free glass, lead-containing glass, borosilicate glass, aluminosilicate glass, low expansion glass, quartz glass and the like. When the transfer process of the present invention is carried out in vacuum, a glass plate is a particularly preferable support 31 because it is required that gas release from the support is small.

  Even if the photothermal conversion layer 33 is heated to a high temperature, the temperature rise (thermal expansion) of the support 31 itself needs to be within an allowable range, so that the heat capacity of the support 31 is sufficiently larger than that of the photothermal conversion layer 33. Is preferred. Accordingly, the thickness of the support 31 is preferably 10 times or more the thickness of the photothermal conversion layer 33. Although the allowable range of thermal expansion depends on the size of the transfer region and the required accuracy of patterning, it cannot be generally shown. For example, the photothermal conversion layer 33 rises by 300 ° C. from room temperature, and the temperature rise of the support 31 When it is desired to suppress the temperature to 1/100, which is 3 ° C. or less, the thickness of the support 31 is preferably 100 times or more the thickness of the photothermal conversion layer 33, and the temperature rise of the support 31 is 1 ° C. at 300 ° C. When it is desired to suppress the temperature to 1 ° C. or less, which is / 300, the thickness of the support 31 is preferably 300 times or more the thickness of the photothermal conversion layer 33. By doing so, even if the donor substrate 30 is enlarged, the amount of dimensional displacement due to thermal expansion is small, and highly accurate patterning becomes possible.

  In the donor substrate 30 according to the first embodiment, the photothermal conversion layer 33 is a layer formed on the support 31 and efficiently absorbs light to generate heat and is stable against the generated heat. If it is a certain material and composition, it will not be limited in particular. However, in order to prevent a rapid temperature rise and prevent a local temperature drop due to thermal diffusion to the partition pattern 34, it is desirable that the heat capacity is large.

This is because if the heat capacity of the high heat conversion layer 33 is small, the transfer layer 37 cannot be transferred slowly because it is easy to heat and cool. The heat capacity is a product of volume and volume specific heat, and a material having a large volume specific heat is desirable. Specifically, the volume specific heat of the photothermal conversion layer 33 is preferably 2 J / cm ³ K or more. Further, a larger heat conductivity of the photothermal conversion layer 33 is more desirable because uniform heating is possible and local temperature decrease is reduced. Specifically, the thermal conductivity of the photothermal conversion layer 33 is preferably 50 W / mK or more. The photothermal conversion layer 33 may be a layer made of a single material or a layer made of an alloy, and may be a single layer or a plurality of layers in which a plurality of materials are laminated.

  Here, in the case where the photothermal conversion layer 33 is made of a plurality of layers or alloys of different materials, the thermal conductivity and the volume specific heat are values of the entire photothermal conversion layer. As the overall value, in the case of a plurality of laminated thin films made of different materials, a calculated value obtained by weighting and averaging the values of the thermal conductivity and volume specific heat of the material alone with the respective film thicknesses is used. When calculation is difficult like an alloy, it can be measured by a known method such as a laser flash method, a scanning laser AC heating method, a differential method, or a 3ω method.

  As a material used for the high heat conversion layer 33, a thin film in which carbon black, graphite, titanium black, an organic pigment, metal particles, or the like is dispersed in a resin can be used. Moreover, in this Embodiment 1, since the photothermal conversion layer 33 may be heated to about 300 degreeC, the photothermal conversion layer 33 is excellent in heat resistance, and consists of an inorganic thin film with high heat conductivity and volume specific heat. preferable. Therefore, it is particularly preferable to use a metal thin film in terms of light absorption and film formability. Specifically, as a metal material, tungsten, tantalum, molybdenum, titanium, chromium, gold, silver, copper, platinum, iron, zinc, aluminum, cobalt, nickel, magnesium, vanadium, zirconium, silicon, carbon, etc. Or a thin film of an alloy or a laminated thin film thereof can be used.

  As a method for forming the photothermal conversion layer 33, a known technique such as vacuum vapor deposition, EB vapor deposition, sputtering, ion plating, or the like can be used. When patterning, a known method such as a laser ablation method can be used.

  It is preferable that the photothermal conversion layer 33 has a fine uneven structure on the surface, that is, the surface is rough. The first embodiment is characterized in that the siloxane composition, which is the material of the partition pattern 34, has an inorganic property, so that it is easy to form a chemical bond with the metal, which is the material of the photothermal conversion layer 33. Here, when the surface of the light-to-heat conversion layer 33 is roughened as shown in FIG. 1, compared with the case where the surface of the light-to-heat conversion layer 33 is smooth as shown in FIG. By increasing the adhesion surface area, it is possible to further improve the adhesion.

  Further, by making the surface of the light-to-heat conversion layer 33 rough, when a solution containing a transfer material is applied to the donor substrate 30, local film thickness unevenness in the dried film can be prevented. An effect is also produced. FIG. 3 is a diagram illustrating the formation of a dry film of the transfer material when the solution containing the transfer material is applied to the donor substrate 30. When a substrate having a light-to-heat conversion layer 33 having a smooth surface as shown in FIG. 3A is used, film thickness unevenness due to a so-called “coffee stain” phenomenon may occur. That is, when a solution containing a transfer material is dropped, the solvent drying speed is faster at the periphery of the droplet than at the center, so that the solvent flows from the center to the periphery to compensate for the liquid that evaporates from the periphery. . At this time, the solute (transfer material) is also carried to the peripheral portion along this flow, and as a result, a film having a shape in which the peripheral portion is raised is formed.

  On the other hand, as shown in FIG. 3B, when the donor substrate 30 having a rough surface of the photothermal conversion layer 33 is used, the movement of the solution from the center to the peripheral portion is prevented by the unevenness of the surface of the photothermal conversion layer 33. The Therefore, the solute tends to be uniformly dispersed and deposited on the surface of the donor substrate 30, and local film thickness unevenness can be suppressed. Even if a slight film thickness unevenness following the unevenness of the light-to-heat conversion layer 33 is present in the transfer layer 37, the transfer material is brought to the molecular (atomic) level during transfer by using the vapor deposition mode described later. Since the film is deposited on the device substrate 20 after sublimation in a loose state, the film thickness unevenness of the transfer film 27 is made uniform, and the light emission luminance unevenness when the organic EL element is manufactured does not become a problem.

  The degree of roughness of the photothermal conversion layer 33 can be represented by an arithmetic surface roughness (hereinafter referred to as Ra) of the surface of the photothermal conversion layer 33. In addition, the arithmetic average roughness in the present invention is a ten-point average roughness obtained when measured with a measurement length of 1.0 mm based on JIS B0601-1994 using a surface roughness shape measuring instrument. In the present invention, as the actual surface area of the photothermal conversion layer 33 is larger, the bond with the partition pattern 34 is increased and the adhesion is improved. Therefore, the surface Ra of the photothermal conversion layer 33 is preferably larger, and preferably 30 nm or more. . More preferably, it is 50 nm or more, More preferably, it is 100 nm or more, Most preferably, it is 150 nm or more. By taking the above numerical values, the effect can also be exhibited in suppressing the film thickness unevenness of the transfer layer 37.

  On the other hand, if Ra on the surface of the light-to-heat conversion layer 33 is too large, the solution accumulates in the recess when a solution containing a transfer material is applied. There arises a problem that the film thickness unevenness increases. In order to prevent the solution from accumulating in the recesses, the thickness of the coating solution only needs to be larger than Ra on the surface of the photothermal conversion layer 33. Specifically, Ra of the photothermal conversion layer 33 is preferably 4 μm or less, more preferably 1 μm or less, still more preferably 500 nm or less, and particularly preferably 250 nm or less. Within this range, the thickness of the coating solution can be made larger than the Ra of the photothermal conversion layer 33 when a solution having a reasonable concentration is applied to obtain a transfer material having a desired thickness. .

  Further, in order to achieve both the adhesion between the lower part of the partition pattern 34 and the light-to-heat conversion layer 33 and the film uniformity of the transfer layer 37, the Ra of the part forming the transfer layer 37 and the Ra of the lower part of the partition pattern 34 are appropriately changed. May be. That is, as the actual surface area of the light-to-heat conversion layer 33 is larger, the bond with the partition pattern 34 is increased and the adhesion is improved. Therefore, it is preferable that the surface Ra of the light-to-heat conversion layer 33 is larger, but on the other hand, the area where the transfer material is formed If Ra is also increased, the solution accumulates in the recesses when a solution containing a transfer material is applied. Therefore, the dried film becomes discontinuous, and the film thickness unevenness after transfer to the device substrate increases. Therefore, as shown in FIG. 4, a configuration may be adopted in which Ra at the bottom of the partition pattern 34 is increased and Ra in the area where the transfer material is formed is decreased.

  There are roughly two methods for roughening the surface of the photothermal conversion layer 33. One is a method in which the photothermal conversion layer 33 is formed substantially uniformly on the support 31 roughened in advance according to the unevenness of the surface of the support 31. In the case of this method, Ra on the surface of the support 31 can be copied to Ra on the surface of the photothermal conversion layer 33. For example, by setting Ra on the surface of the support 31 to be 30 nm or more, Ra on the surface of the photothermal conversion layer 33 can be adjusted to 30 nm or more. Therefore, it is preferable that the Ra on the surface of the support 31 on which the light-to-heat conversion layer 33 is formed is set to a value obtained as Ra on the surface of the light-to-heat conversion layer 33. For example, it is preferably 30 nm or more, more preferably 50 nm or more, still more preferably 100 nm or more, and particularly preferably 150 nm or more.

  The method of roughening the surface of the support 31 is not particularly limited. Mechanical roughening by sandblasting, chemical etching by hydrofluoric acid, buffered hydrofluoric acid and mixed acids with other acids, and glass powder are applied to the surface. Well-known techniques such as a method of welding with high heat can be used. In these treatments, Ra increases as the conditions such as pressure and treatment time are increased, so that the desired Ra can be adjusted.

  As a method for forming the photothermal conversion layer 33 substantially uniformly according to the irregularities on the surface of the support 31, a sputtering method is preferably exemplified. Although detailed conditions differ depending on the material, it cannot be generally stated, but as an example, in the case of tantalum, for example, it is preferable to form it in an Ar gas atmosphere with a gas pressure of 0.2 Pa and an input power of 1 kw. Of course, the condition is not limited to this.

  Another method of roughening the surface of the photothermal conversion layer 33 is a method of roughening the surface after forming the photothermal conversion layer 33 having a substantially smooth surface by a known method. The method is not particularly limited, and publicly known techniques such as mechanical surface roughening by sandblasting, chemical etching, and gas pressure / input power / film formation temperature change during sputtering film formation can be used.

  However, in the method of directly roughening the photothermal conversion layer 33, the surface temperature varies between the thick and thin portions of the photothermal conversion layer when light irradiation is performed, and the transfer material is uniformly heated. For this reason, the former method in which the surface of the support 31 is roughened and the photothermal conversion layer 33 is uniformly formed according to the unevenness of the surface is preferable.

  The partition pattern 34 defines the size (compartment) of a transfer layer 37 described later, and is formed on the photothermal conversion layer 33. The partition pattern 34 according to the first embodiment is formed from a siloxane composition including a siloxane polymer (A) obtained by reacting at least one siloxane compound represented by the following general formula (1). Moreover, it is preferable that the content rate of a phenolic hydroxyl group is 0.2 mol or less with respect to 1 mol of Si atoms in a siloxane polymer (A).

In General Formula (1), R ¹ is hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 16 carbon atoms, and R ² is hydrogen or carbon number An alkyl group having 1 to 10 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms. n is an integer of 0-3. When a plurality of R ¹ and R ² are present, they may be the same or different.
In the above R ¹ and R ² , examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n- Decyl group, trifluoromethyl group, 3,3,3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-aminopropyl group, 3-mercaptopropyl Group, 3-isocyanatopropyl group and the like.

In R ¹ , examples of the alkenyl group having 2 to 10 carbon atoms include a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group.
In the above R ¹ and R ² , the aryl group having 6 to 15 carbon atoms includes phenyl group, tolyl group, p-hydroxyphenyl group, 1- (p-hydroxyphenyl) ethyl group, 2- (p-hydroxyphenyl) Examples thereof include an ethyl group, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl group, and naphthyl group.
In R ² described above, examples of the acyl group having 1 to 6 carbon atoms include an acetyl group, a formyl group, and a propionyl group.

  Specific examples of the siloxane compound represented by the general formula (1) include tetrafunctional silane having four alkoxy groups such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane, methyltrimethoxysilane, Methyltriethoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n- Propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, Nyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxy Silane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 having three alkoxy groups such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane Bifunctional silane having two alkoxy groups such as functional silane, dimethyldimethoxysilane, dimethyldiethoxylane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, trimethylmethoxysilane, tri-n- And monofunctional silanes having one alkoxy group such as butylethoxysilane.

  Of the siloxane compounds represented by the general formula (1), trifunctional silanes having three alkoxy groups where n is 3 are preferred. By using trifunctional silane, the crack resistance and hardness of each pattern can be improved. The siloxane compound represented by the general formula (1) may be used alone or in combination of two or more. Examples of the combination of two or more siloxane compounds represented by the general formula (1) include methyltrimethoxysilane and phenyltrimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane and 4-hydroxy-5- (p -Hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

The siloxane polymer (A) according to the first embodiment reacts at least one siloxane compound represented by the general formula (1) with a linear siloxane compound represented by the following general formula (3). It may be made.
In General Formula (3), R ⁶ , R ⁷ , R ⁸ , and R ⁹ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 6 to 6 carbon atoms. 16 aryl groups. R ¹⁰ and R ¹¹ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms. m is a natural number of 1-1000. When a plurality of R ⁶ and R ⁷ are present, they may be the same or different.

In the above R ^{6 to} R ¹¹ , examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n- Decyl group, trifluoromethyl group, 3,3,3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-aminopropyl group, 3-mercaptopropyl Group, 3-isocyanatopropyl group and the like.

In R ^{6 to} R ⁹ , examples of the alkenyl group having 2 to 10 carbon atoms include a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group.
In the above R ^{6 to} R ¹¹ , the aryl group having 6 to 15 carbon atoms includes a phenyl group, a tolyl group, a p-hydroxyphenyl group, a 1- (p-hydroxyphenyl) ethyl group, and 2- (p-hydroxyphenyl). Examples thereof include an ethyl group, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl group, and naphthyl group.
In R ¹⁰ and R ¹¹ , examples of the acyl group having 1 to 6 carbon atoms include an acetyl group, a formyl group, and a propionyl group.
In General formula (3), m is a natural number of 1-1000, Preferably, it is 2-100, 3-50 are especially preferable.

  Specific examples of the linear siloxane compound represented by the general formula (3) include 1,1,3,3-tetramethyl-1,3-dimethoxydisiloxane, 1,1,3,3-tetramethyl-1 , 3-diethoxydisiloxane, 1,1,3,3-tetraethyl-1,3-dimethoxydisiloxane, 1,1,3,3-tetraethyl-1,3-diethoxydisiloxane, Gerest Corporation shown below Silanol-terminated polydimethylsiloxane (trade name) "DMS-S12" (molecular weight 400-700), "DMS-S15" (molecular weight 1500-2000), "DMS-S21" (molecular weight 4200), "DMS-S27" ( Molecular weight 18000), “DMS-S31” (molecular weight 26000), “DMS-S32” (molecular weight 36000), “DMS-S33” (molecular weight 43500), DMS-S35 "(molecular weight 49000)," DMS-S38 "(molecular weight 58000)," DMS-S42 "(molecular weight 77000), and the following silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer" PDS-0332 "(molecular weight) 35000, 2.5-3.5 mol% of diphenylsiloxane is copolymerized), “PDS-1615” (molecular weight 900-1000, 14-18 mol% of diphenylsiloxane is copolymerized), manufactured by Gerest And silanol-terminated polydiphenylsiloxane "PDS-9931" (molecular weight 1000-1400).

By using the linear siloxane compound represented by the general formula (3), it has excellent effects in all of storage stability, crack resistance, heat resistance, transparency, low dielectric constant, and high hardness. In particular, the storage stability is excellent. The linear siloxane compound represented by the general formula (3) is linear, and the linear siloxane compound represented by the general formula (3) and the general formula ( In the partial condensate with the siloxane compound represented by 1), the linear siloxane compound represented by the general formula (3) is present as a bridge, so that the condensation reaction of unreacted silanol groups during storage is suppressed. Presumed to be possible. Examples of suitable combinations of the siloxane compound represented by the general formula (1) and the linear siloxane compound represented by the general formula (3) include methyltrimethoxysilane, phenyltrimethoxysilane, and DMS-S12. Is exemplified.
The mixing ratio in the case of using the siloxane compound represented by the general formula (1) and the linear siloxane compound represented by the general formula (3) is not particularly limited, but is preferably the number of moles of Si atoms. Siloxane compound / linear siloxane compound = 100/0 to 50/50. If the amount of the linear siloxane compound is more than 50 mol%, phase separation may occur.

  Further, the siloxane polymer (A) according to the first embodiment includes silica particles other than the siloxane compound represented by the general formula (1) and the linear siloxane compound represented by the general formula (3). It is preferable to synthesize by mixing and reacting. The pattern resolution is further improved by mixing and reacting silica particles. This is presumably because silica particles are incorporated into the polymer, so that the glass transition temperature of the film is increased and the pattern dripping at the time of thermosetting is suppressed.

  The number average particle diameter of the silica particles to be mixed is preferably 2 nm to 200 nm, and more preferably 5 nm to 70 nm. The number average particle diameter of the silica particles can be measured using various particle counters.

  As silica particles to be mixed, for example, IPA-ST having a particle diameter of 12 nm using isopropanol as a dispersant, MIBK-ST having a particle diameter of 12 nm using methyl isobutyl ketone as a dispersant, and IPA-ST having a particle diameter of 45 nm using isopropanol as a dispersant. ST-L, IPA-ST-ZL having a particle size of 100 nm using isopropanol as a dispersant, PGM-ST having a particle size of 15 nm using propylene glycol monomethyl ether as a dispersant (manufactured by Nissan Chemical Industries, Ltd.), γ- "Oscar (registered trademark)" 101 (particle size 12 nm) using butyrolactone as a dispersant, "Oscar (registered trademark)" 105 (particle size 60 nm) using γ-butyrolactone as a dispersant, and diacetone alcohol as a dispersant. "Oscar (registered trademark)" 106 (particle size 120 nm) (above, catalyzed "Quartron (registered trademark)" PL-2L-PGME (particle diameter 16 nm) using propylene glycol monomethyl ether as a dispersant, and "Quartron (registered trademark)" using γ-butyrolactone as a dispersant. PL-2L-BL (particle diameter: 17 nm), “Quatron (registered trademark)” PL-2L-DAA (particle diameter: 17 nm) (made by Fuso Chemical Industry Co., Ltd.) using diacetone alcohol as a dispersant It is done. In addition, these silica particles may be used alone or in combination of two or more.

  The mixing ratio in the case of using silica particles is not particularly limited, but is preferably 30 mol% or less in terms of the number of moles of Si atoms relative to the number of moles of Si atoms in the entire siloxane polymer (A). This is because when the amount of silica particles is more than 30 mol%, the compatibility between the siloxane polymer (A) and the quinonediazide compound (B) described later is deteriorated. The Si atom molar ratio of the silica particles to the total number of Si atoms of the siloxane polymer (A) is determined by 29Si-NMR measurement of the polymer, and the Si peak area of the silica particles and the Si peaks other than the silica particles in the obtained spectrum. It can be determined from the ratio with the area. In addition, in the siloxane polymer (A), from the viewpoint of achieving both crack resistance and hardness of the partition pattern 34, the phenyl group content in the siloxane polymer (A) is 0.05 to 1 mol per mole of Si atoms. It is preferable that it is 0.6 mol, More preferably, it is 0.1-0.45 mol. When the phenyl group content is more than 0.6 mol, the hardness of the partition pattern 34 is lowered, and when the phenyl group content is less than 0.05 mol, the crack resistance of the partition pattern 34 is lowered. The phenyl group content is measured, for example, by measuring the 29Si-nuclear magnetic resonance spectrum (NMR) of the siloxane polymer (A), and the peak area of Si to which the phenyl group is bonded and the peak area of Si to which the phenyl group is not bonded. It can be obtained from the ratio.

  The mass average molecular weight (Mw) of the siloxane polymer (A) used in the first embodiment is not particularly limited, but is preferably 1000 to 100,000 in terms of polystyrene measured by GPC (gel permeation chromatography), more preferably 2000 to 50000. When Mw is less than 1000, the coating properties are deteriorated, and when it is more than 100,000, the solubility in a developing solution during pattern formation is deteriorated.

  The siloxane polymer (A) of Embodiment 1 is obtained by hydrolyzing and partially mixing a mixture of the siloxane compound represented by the above formula (1), the linear siloxane compound represented by the formula (3), and silica particles. Obtained by condensation. A general method can be used for hydrolysis and partial condensation. For example, a solvent, water, and a catalyst as required are added to the mixture, and the mixture is heated and stirred at 50 to 150 ° C. for about 0.5 to 100 hours. During the stirring, hydrolysis by-products (alcohols such as methanol) and condensation by-products (water) may be distilled off by distillation as necessary.

  Although there is no restriction | limiting in particular as said reaction solvent, Usually, the thing similar to the compound which has an alcoholic hydroxyl group and / or the cyclic compound (C) which has a carbonyl group as a solvent mentioned later is used. The addition amount of the solvent is preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the mixture of the siloxane compound represented by formula (1) and the linear siloxane compound represented by formula (3). The amount of water used for the hydrolysis reaction is preferably 0.5 to 2 mol with respect to 1 mol of the hydrolyzable group. In addition, also when mixing a silica particle in the said siloxane compound, the preferable addition amount of a solvent is the same range.

  Although there is no restriction | limiting in particular in the catalyst added as needed, An acid catalyst and a base catalyst are used preferably. Specific examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyvalent carboxylic acid or anhydride thereof, and ion exchange resin. Specific examples of the base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, amino Examples include alkoxysilanes having groups and ion exchange resins. The addition amount of the catalyst is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the mixture of the siloxane compound represented by the formula (1) and the linear siloxane compound represented by the formula (3).

  Further, from the viewpoint of coating properties and storage stability, it is preferable that the siloxane polymer (A) solution after hydrolysis and partial condensation does not contain alcohol, water, and catalyst as by-products. Therefore, these removals may be performed as necessary. Although there is no restriction | limiting in particular as a removal method, Preferably removal is performed with the following method. As a method for removing alcohol or water, there can be used a method in which an organic layer obtained by diluting a siloxane polymer (A) solution with an appropriate hydrophobic solvent and then washing several times with water is concentrated with an evaporator. Further, as a method for removing the catalyst, in addition to the above water washing, a method of treating with an ion exchange resin alone can be used.

  Further, by using the siloxane polymer (A) as the siloxane composition forming the partition pattern 34 of the first embodiment, the adhesion with the photothermal conversion layer 33 can be improved. In order to improve the linearity and smoothness of 34, it is preferable to contain a quinonediazide compound (B). The quinonediazide compound (B) is a naphthoquinonediazidesulfonic acid ester of a compound having a phenolic hydroxyl group, and the ortho position and the para position of the phenolic hydroxyl group are each independently represented by hydrogen or the following general formula (2). And a substituent having a structure.

In General Formula (2), R ³ , R ⁴ , and R ⁵ are each independently an alkyl group having 1 to 10 carbon atoms, a carboxyl group, or a phenyl group that may have a substituent, R ³ , R ⁴ and R ⁵ may combine to form a ring.
In R ^{3 to} R ⁵ , the alkyl group having 1 to 10 carbon atoms includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-hexyl group. , A cyclohexyl group, an n-heptyl group, an n-octyl group, an n-decyl group, a trifluoromethyl group, and a 2-carboxyethyl group having a substituent such as a carboxyl group.

In the above R ^{3 to} R ⁵ , examples of the carboxyl group include an acetyl group, a formyl group, and a propionyl group.
Examples of the phenyl group that may have a substituent in R ^{3 to} R ⁵ include a phenyl group and a p-hydroxyphenyl group.
R ³ , R ⁴ and R ⁵ may be bonded to form a ring. For example, any two of R ³ , R ⁴ and R ⁵ may be bonded to form a cyclopentane ring, cyclohexane ring, adamantane. What formed the ring and the fluorene ring can be illustrated.

  When the ortho-position and para-position of the phenolic hydroxyl group of the quinonediazide compound (B) are substituents other than the above, for example, a methyl group, oxidative decomposition occurs due to thermal curing at the time of formation of the partition pattern 34, and is represented by a quinoid structure. A conjugated compound is formed, and the partition pattern 34 is colored. These quinonediazide compounds (B) can be synthesized by a known esterification reaction between a compound having a phenolic hydroxyl group and naphthoquinonediazidesulfonic acid chloride.

  Specific examples of the compound having a phenolic hydroxyl group include the following compounds (trade name, manufactured by Honshu Chemical Industry Co., Ltd.).

  As naphthoquinone diazide sulfonic acid, 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid can be used. Since 4-naphthoquinonediazide sulfonic acid ester compound has absorption in the i-line (wavelength 365 nm) region, it is suitable for i-line exposure. Moreover, since 5-naphthoquinone diazide sulfonic acid ester compound has absorption in a wide range of wavelengths, it is suitable for exposure in a wide range of wavelengths. It is preferable to select a 4-naphthoquinone diazide sulfonic acid ester compound or a 5-naphthoquinone diazide sulfonic acid ester compound depending on the wavelength to be exposed. A 4-naphthoquinone diazide sulfonic acid ester compound and a 5-naphthoquinone diazide sulfonic acid ester compound may be mixed and used.

Although there is no restriction | limiting in particular in the addition amount of a quinonediazide compound (B), Preferably it is 0.1-10 mass parts with respect to 100 mass parts of siloxane polymers (A). When the addition amount of the quinonediazide compound (B) is less than 0.1 parts by mass, it may not have photosensitivity. When the addition amount of the quinonediazide compound (B) is more than 10 parts by mass, the transparency of the partition pattern 34 is lowered.
The molecular weight of the naphthoquinone diazide compound (B) is preferably 300 to 1500, and more preferably 350 to 1200. If the molecular weight of the naphthoquinone diazide compound (B) is more than 1500, pattern formation may not be possible with an addition amount of 0.1 to 10 parts by mass or 0.1 to 4 parts by mass. On the other hand, when the molecular weight of the naphthoquinone diazide compound (B) is smaller than 300, the colorless transparency may be lowered.

  The siloxane composition of Embodiment 1 preferably contains a compound having an alcoholic hydroxyl group and / or a cyclic compound (C) having a carbonyl group as a solvent. When these compounds (C) are used as a solvent, the siloxane polymer (A) and the quinonediazide compound (B) are uniformly dissolved, and the partition polymer 34 is not whitened when the siloxane composition is applied and formed into a film.

Although there is no restriction | limiting in particular in the compound which has alcoholic hydroxyl group, Preferably it is a compound whose boiling point under atmospheric pressure is 110-250 degreeC. When the boiling point is higher than 250 ° C., the amount of residual solvent in the partition polymer 34 increases, so that shrinkage during curing increases, and good flatness cannot be obtained. On the other hand, if the boiling point is lower than 110 ° C., the coating properties deteriorate, such as drying at the time of coating is too fast and the film surface becomes rough.
Specific examples of the compound having an alcoholic hydroxyl group include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy- 4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono -T-butyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol. Among these, a compound further having a carbonyl group is preferable, and diacetone alcohol is particularly preferably used. These compounds having an alcoholic hydroxyl group may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular in the cyclic compound which has a carbonyl group, Preferably it is a compound whose boiling point under atmospheric pressure is 150-250 degreeC. When the boiling point is higher than 250 ° C., the amount of residual solvent in the partition polymer 34 increases, so that shrinkage during curing increases, and good flatness cannot be obtained. On the other hand, if the boiling point is lower than 150 ° C., the coating properties deteriorate, for example, drying at the time of coating is too fast and the film surface becomes rough. Specific examples of the cyclic compound having a carbonyl group include γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, and cycloheptanone. Among these, γ-butyrolactone is particularly preferably used. These cyclic compounds having a carbonyl group may be used alone or in combination of two or more.

  The above compound having an alcoholic hydroxyl group and the cyclic compound (C) having a carbonyl group may be used alone or in combination. When mixed and used, the mass ratio is not particularly limited, but is preferably a compound having an alcoholic hydroxyl group / a cyclic compound having a carbonyl group = 99/1 to 50/50, more preferably 97/3 to 60/40. It is. If the compound having an alcoholic hydroxyl group is more than 99% by mass (the cyclic compound having a carbonyl group is less than 1% by mass), the compatibility between the siloxane polymer (A) and the quinonediazide compound (B) is poor, and the cured film is white. Transparency decreases. Further, when the compound having an alcoholic hydroxyl group is less than 50% by mass (the cyclic compound having a carbonyl group is more than 50% by mass), the condensation reaction of the unreacted silanol group in the siloxane polymer (A) is likely to occur and storage. Stability deteriorates.

Moreover, the siloxane composition concerning this Embodiment 1 may contain another solvent, unless the effect of this invention is impaired. Other solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy- Examples thereof include esters such as 1-butyl acetate, ketones such as methyl isobutyl ketone, diisopropyl ketone and diisobutyl ketone, and ethers such as diethyl ether, diisopropyl ether, di n-butyl ether and diphenyl ether.
The amount of the solvent added is preferably in the range of 100 to 1000 parts by mass with respect to 100 parts by mass of the siloxane polymer (A).

  Furthermore, the siloxane composition according to the first embodiment may contain a sensitizer. The sensitizer at this time is preferably a sensitizer which is vaporized by heat treatment and / or discolored by light irradiation. In general, sensitizers are often used to improve sensitivity, but conventionally used sensitizers are compounds that absorb the energy of a wide range of wavelengths of radiation and transfer the energy to other substances. Various substituents have been introduced to absorb radiation over a wide range of wavelengths. However, conventional sensitizers are difficult to use in fields where high transparency is required because they absorb visible light, decompose or color by heat treatment. In particular, a sensitizer that does not absorb visible light with respect to a mixed line having an exposure wavelength of 365 nm (i-line), 405 nm (h-line), and 436 nm (g-line) cannot be expected to increase sensitivity, and is in the visible light region. Sensitizers that absorb light can be expected to have high sensitivity, but the colorless transparency in the visible light region tends to decrease. Therefore, it is vaporized by heat treatment and / or light-irradiated with the idea that even if it is vaporized by heat treatment and does not cause coloring by the sensitizer, or remains in the resin film, it does not fade and cause coloration by light irradiation. By using a sensitizing agent that fades, high sensitivity can be achieved while maintaining high transparency.

  Specific examples of the sensitizer that is vaporized by the heat treatment and / or faded by light irradiation include coumarins such as 3,3′-carbonylbis (diethylaminocoumarin), anthraquinones such as 9,10-anthraquinone, benzophenone, Aromatic ketones such as 4,4′-dimethoxybenzophenone, acetophenone, 4-methoxyacetophenone, benzaldehyde, biphenyl, 1,4-dimethylnaphthalene, 9-fluorenone, fluorene, phenanthrene, triphenylene, pyrene, anthracene, 9-phenylanthracene, 9-methoxyanthracene, 9,10-diphenylanthracene, 9,10-bis (4-methoxyphenyl) anthracene, 9,10-bis (triphenylsilyl) anthracene, 9,10-dimethoxya Tracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentaoxyanthracene, 2-t-butyl-9,10-dibutoxyanthracene, 9 , 10-bis (trimethylsilylethynyl) anthracene and the like.

  Among these sensitizers, the sensitizer that is vaporized by heat treatment is preferably a sensitizer that sublimates or evaporates a thermal decomposition product by sublimation, evaporation, and thermal decomposition. Moreover, as vaporization temperature of a sensitizer, Preferably it is 130 to 400 degreeC, More preferably, it is 150 to 250 degreeC. When the vaporization temperature of the sensitizer is lower than 130 ° C., the sensitizer is vaporized during the pre-bake and does not exist during the exposure process, so that high sensitivity cannot be achieved. In order to suppress vaporization during prebaking as much as possible, the vaporization temperature of the sensitizer is preferably 150 ° C. or higher. On the other hand, if the vaporization temperature of the sensitizer is higher than 400 ° C., the sensitizer does not vaporize during thermal curing and remains in the cured film, resulting in a decrease in colorless transparency. Moreover, in order to vaporize completely at the time of thermosetting, the vaporization temperature of a sensitizer is preferably 250 ° C. or less.

On the other hand, the sensitizer that fades by light irradiation is preferably a sensitizer whose absorption in the visible light region fades by light irradiation from the viewpoint of transparency. Further, a compound that fades upon irradiation with light is a compound that dimerizes upon irradiation with light. By dimerization by light irradiation, the molecular weight increases to insolubilize, so that the effect of improving chemical resistance, improving heat resistance, and reducing the extract from the partition pattern 34 can be obtained.
The sensitizer is preferably an anthracene compound in that it can achieve high sensitivity and dimerizes and fades when irradiated with light, and the anthracene compound in which the 9th and 10th positions are hydrogen is unstable to heat. Therefore, a disubstituted anthracene compound in which at least 9,10 is substituted is preferable. Furthermore, it is preferable that it is a 9,10- dialkoxy anthracene type compound represented by General formula (4) from a viewpoint of the improvement of the solubility of a sensitizer, and the reactivity of a photodimerization reaction.

In formula (4), R ^{12 to} R ¹⁹ each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group, an alkenyl group, an ethynyl group, an aryl group, an acyl group, or a group in which they are substituted. Represents an organic group. R ²⁰ and R ²¹ each independently represent an alkoxy group having 1 to 20 carbon atoms and an organic group in which they are substituted.

In R ^{12 to} R ¹⁹ , examples of the alkyl group include a methyl group, an ethyl group, and an n-propyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group. Examples of the alkenyl group include a vinyl group, an acryloxypropyl group, and a methacryloxypropyl group. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. Examples of the acyl group include an acetyl group. From the viewpoint of the vaporization property of the compound and the photodimerization reactivity, R ^{12 to} R ¹⁹ are preferably hydrogen or an organic group having 1 to 6 carbon atoms. More preferably, R ^{12 to} R ¹⁹ are preferably hydrogen.

In the above R ²⁰ and R ²¹ , examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, etc., but the solubility and photodimerization of the compound represented by the general formula (4) From the viewpoint of the fading reaction due to, a propoxy group and a butoxy group are preferable.
When using a sensitizer, it is preferable to add in 0.01-5 mass parts with respect to 100 mass parts of siloxane polymers (A). If it is out of this range, the transparency is lowered and the sensitivity is lowered.

  Furthermore, the siloxane composition according to the first embodiment may contain a thermal acid generator. By containing a thermal acid generator, an acid is generated during thermosetting, and unreacted silanol groups in the siloxane polymer (A) are condensed, and the hardness of the partition pattern 34 is improved. As the thermal acid generator, it is necessary to use a non-photosensitive mercury lamp which is exposure light (particularly i-line (wavelength 365 nm), h-line (wavelength 405 nm), g-line (wavelength 436 nm)), and benzylsulfonium salt. A sulfonimide compound is preferred. As specific examples, “Sun-Aid (registered trademark)” SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, SI-100L, SI-110L, SI- 145L, SI-150L, SI-160L, SI-180L (manufactured by Sanshin Chemical Industry Co., Ltd.), 4-hydroxyphenyldimethylsulfonium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenyldimethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenylbenzylmethylsulfonium trifluoromethanesulfonate, 4 Methoxycarbonyloxyphenyldimethylsulfonium trifluoromethanesulfonate, benzyl-4-methoxycarbonyloxyphenylmethylsulfonium trifluoromethanesulfonate (trade name, manufactured by Sanshin Chemical Industry Co., Ltd.), SI-101, SI-105, SI -106, SI-109, PI-105, NDI-101, NDI-105, NDI-109 (above, trade name, manufactured by Midori Chemical Co., Ltd.).

  The amount of the thermal acid generator added is preferably in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the siloxane polymer (A). Beyond this range, care must be taken because the hardness of the partition pattern 34 decreases and cracks occur.

The siloxane composition of the present invention may contain additives such as a dissolution accelerator, a dissolution inhibitor, a thermosetting agent, a surfactant, a stabilizer, and an antifoaming agent as necessary.
In particular, dissolution promoters are often used for the purpose of improving sensitivity. As the dissolution accelerator, a compound having a phenolic hydroxyl group or an N-hydroxydicarboximide compound is preferably used. Specific examples include compounds having a phenolic hydroxyl group used for the quinonediazide compound.

  As a method of forming the partition pattern 34, the partition pattern 34 having excellent linearity and smoothness can be formed by applying the siloxane composition described above on the photothermal conversion layer 33 and then patterning it by a photolithography method. it can. When the quinonediazide compound (B) is not blended as the siloxane composition, the partition pattern 34 may be formed by a lift method or a dry etching method.

  First, the siloxane composition according to the first embodiment is applied on the support 31 on which the photothermal conversion layer 33 is formed by a known method such as a spinner, dipping, or slit, and prebaked with a heating device such as a hot plate or oven. . Pre-baking is performed in the range of 50 to 150 ° C. for 30 seconds to 30 minutes, and the film thickness after pre-baking is preferably 0.1 to 15 μm.

  After pre-baking, using a UV-visible exposure machine such as a stepper, mirror projection mask aligner (MPA), parallel light mask aligner (PLA), etc., expose about 10 to 4000 J / m2 (wavelength 365 nm exposure equivalent) through the desired mask. To do.

  After the exposure, the exposed portion can be dissolved by development to obtain a positive pattern. As a developing method, it is preferable to immerse in a developer for 5 seconds to 10 minutes by a method such as showering, dipping or paddle. As the developer, a known alkali developer can be used. Specific examples include alkali metal hydroxides, carbonates, phosphates, silicates, borates, and other inorganic alkalis, amines such as 2-diethylaminoethanol, monoethanolamine, diethanolamine, and tetramethyl hydroxide. Examples include aqueous solutions containing one or more quaternary ammonium salts such as ammonium and choline.

After development, it is preferable to rinse with water, followed by drying and baking in the range of 50 to 150 ° C.
Thereafter, it is preferable to perform bleaching exposure. By performing bleaching exposure, the unreacted quinonediazide compound remaining in the partition pattern 34 can be photolyzed. As a method for bleaching exposure, an entire surface is exposed to about 100 to 20000 J / m ² (wavelength 365 nm exposure amount conversion) using an ultraviolet-visible exposure machine such as PLA.

Then, the division pattern 34 is formed by curing for about 1 hour in the range of 150-450 degreeC with heating apparatuses, such as a hotplate and oven.
The above-described siloxane composition is applied on the support 31 on which the light-to-heat conversion layer 33 is formed, and patterned by a photolithography method, thereby forming a partition pattern 34 having excellent linearity and smoothness as shown in FIG. can do.

  The thickness of the partition pattern 34 is not particularly limited. For example, even if the partition pattern 34 is the same thickness as the transfer layer 37 or thinner, if the gap between the donor substrate 30 and the device substrate is maintained, the transfer material evaporated at the time of transfer is slightly spread and deposited. Therefore, transfer can be performed without causing mixing between adjacent transfer layers 37.

  The sectional shape of the partition pattern 34 is preferably a forward tapered shape in order to facilitate the deposition of the evaporated transfer layer 37 on the device substrate. Here, the “forward taper shape” means a shape in which the sectional width of the partition pattern 34 on the light-to-heat conversion layer 33 side is longer than the width on the upper surface side. As illustrated in FIG. 9 described later, when a pattern such as an insulating layer exists on the device substrate, the width of the insulating layer (the length in the x direction) described later is wider than the width of the partition pattern 34. It is preferable. Further, at the time of alignment, it is preferable to arrange so that the width of the partition pattern 34 falls within the width of the insulating layer. In this case, even if the partition pattern 34 is thin, the donor substrate 30 and the device substrate can be held in a desired gap by increasing the thickness of the insulating layer. The typical width of the partition pattern 34 is 5 to 50 μm and the pitch is 25 to 300 μm. However, the partition pattern 34 may be designed to an optimum value according to the application, and is not particularly limited.

  When applying a transfer method to be described later when arranging the transfer material in the partition pattern 34, the partition material 34 is used in order to prevent the solution from being mixed into another partition or climbing onto the upper surface of the partition pattern 34. Liquid repellent treatment (surface energy control) can be performed on the upper surface of the pattern 34. As the liquid repellent treatment, a method of mixing a liquid repellent material such as a fluorine-based material into the resin material forming the partition pattern 34, or a high concentration region of the liquid repellent material is selected on the surface or upper surface of the partition pattern 34. There is a method of forming.

  An example of the latter case is shown in FIG. (A) shows a case in which the liquid repellent treatment layer 35 is designed wider than the partition pattern 34. Since the solvent after application stays in the partition pattern 34 and is not applied onto the partition pattern 34, the transfer material is used effectively. Can do. (B) shows a case in which the liquid repellent treatment layer 35 is designed to be narrower than the partition pattern 34, and the transfer material wets and spreads on the edge portion on the partition pattern 34, so that a large amount of transfer material is used. Therefore, the thickness uniformity of the light emitting layer after transfer to the device substrate can be improved. Either of these cases can be selected depending on the situation.

  If necessary, an antireflection layer can be formed on the support 31 side of the photothermal conversion layer 33. Further, an antireflection layer may be formed on the surface of the support 31 on the light incident side. These anti-reflection layers are preferably optical interference thin films that use the difference in refractive index, and simple or mixed thin films such as silicon, silicon oxide, silicon nitride, zinc oxide, magnesium oxide, and titanium oxide, and laminated thin films thereof are used. it can.

  The transfer layer 37 is a thin film made of a transfer material formed in a space partitioned by the partition pattern 34. The transfer material may be either an organic material or an inorganic material including a metal. When heated, the transfer material evaporates, sublimates, or ablate sublimates, or uses an adhesive change or volume change to change the device from the donor substrate 30. What is necessary is just to be transcribe | transferred to a board | substrate. Further, the transfer material may be a precursor of the thin film forming material, and the transfer film may be formed by being converted into the thin film forming material by heat or light before or during the transfer.

  The thickness of the transfer layer 37 varies depending on the function and the number of transfers. For example, when transferring a donor material (electron injection material) such as lithium fluoride, a thickness of 1 nm is sufficient, and in the case of an electrode material, the thickness may be 100 nm or more. . In the case of the light emitting layer which is a suitable patterning thin film of the present invention, the thickness of the transfer material is preferably 10 to 100 nm, and more preferably 20 to 50 nm.

  A method for forming the transfer layer 37 is not particularly limited, and a dry process such as vacuum deposition or sputtering can be used. However, as a method that can easily cope with an increase in size, at least a solution composed of a transfer material and a solvent is used as the partition pattern 34. It is preferable to transfer the film after applying it inside and drying the solvent. Examples of the coating method include inkjet, nozzle coating, electropolymerization and electrodeposition, offset and flexographic printing, lithographic printing, relief printing, gravure, screen printing, and other various printing methods. In particular, in the first embodiment, it is important to accurately form a quantitative transfer layer 37 in each partition pattern 34, and from this viewpoint, inkjet can be exemplified as a particularly preferable method.

  When applying a solution consisting of a transfer material and a solvent to the coating method, generally adding a surfactant, dispersant, etc., adjusts the viscosity, surface tension, dispersibility, etc. of the solution to make an ink. Often to do. However, in the first embodiment, if these additives exist as a residue in the transfer layer 37, there is a concern that they are taken into the transfer film even during transfer and adversely affect device performance as impurities. Therefore, it is preferable to minimize the addition or unintentional mixing of these impurities, and it is preferable to prepare the solution so that the purity of the transfer material after drying is 95% or more, and further 98% or more. Such adjustment is possible by setting the ratio of the transfer material in the components other than the solvent in the ink to 95% by mass or more.

  As the solvent, known materials such as water, alcohol, hydrocarbon, aromatic compound, heterocyclic compound, ester, ether, ketone and the like can be used. In the ink jet method suitably used in the present invention, a solvent having a relatively high boiling point of 100 ° C. or higher, more preferably 150 ° C. or higher is used, and the solubility of the organic EL material is excellent. Examples of suitable solvents include methylpyrrolidone (NMP), dimethylimidazolidinone (DMI), γ-butyllactone (γBL), ethyl benzoate, tetrahydronaphthalene (THN), xylene, cumene and the like.

  When the transfer material satisfies all of the solubility, transfer resistance, and device performance after transfer, the transfer material itself (device constituent material) is preferably dissolved in a solvent. When the transfer material has poor solubility in a solvent, the solubility can be improved by introducing a soluble group in the transfer material such as an alkyl group into the solvent. In this specification, such a material is referred to as a precursor of a transfer material (device constituent material). When a soluble group is introduced into a transfer material that is superior in terms of device performance, the performance may deteriorate. In that case, for example, the soluble material can be eliminated by heat at the time of transfer to deposit the original material on the device substrate.

When using a precursor having a soluble group introduced as a transfer material, when transferring the transfer layer 37 made of the transfer material, in order to prevent gas generation and mixing of desorbed substances into the transfer film It is preferable to transfer the transfer material after applying a solution containing the precursor to the partition pattern 34 and then converting or removing the soluble group of the precursor to a transfer material by heat or light.
The transfer donor substrate 30 according to the first embodiment is preferably used as a transfer substrate for a light emitting material of an organic EL element, but forms a thin film constituting a device such as an organic TFT, a photoelectric conversion element, or various sensors. It may be used as a material.

  Next, a method for transferring the transfer layer of the donor substrate to the device substrate in the first embodiment will be described. FIG. 8 is a cross-sectional view showing an example of a method of irradiating the donor substrate with light in the first embodiment. In FIG. 8A, the donor substrate 30 includes a support 31, a photothermal conversion layer 33, a partition pattern 34, and one type of transfer layer 37 existing in the partition pattern 34, and the device substrate 20 includes only the support 21. Become.

  The transfer layer 37 is preferably not in direct contact with the transfer surface of the device substrate 20, and the gap between the transfer layer 37 of the donor substrate 30 and the transfer surface of the device substrate 20 is 1 to 100 μm, and further 2 to 20 μm. It is preferable to keep the range. Therefore, the thickness of the partition pattern 34 is thicker than the thickness of the transfer layer 37 and is preferably 1 to 100 μm, and more preferably 2 to 20 μm. By making the partition pattern 34 having such a thickness face the device substrate 20, the gap between the transfer material of the donor substrate 30 and the transfer target surface of the device substrate 20 can be easily maintained at a constant value, and evaporation can be performed. It is possible to reduce the possibility that the transferred material enters the other compartment.

  The transfer of the transfer layer 37 to the device substrate 20 may be performed by irradiating light typified by laser aiming only at a portion where the transfer layer 37 exists, but as shown in FIG. The light can be incident from the side of the support 31 to irradiate the photothermal conversion layer 33 with light so that at least a part of the transfer layer 37 and at least a part of the partition pattern 34 are simultaneously heated. By adopting such an arrangement, the temperature drop at the boundary between the partition pattern 34 and the transfer layer 37 is suppressed, so that the transfer material existing at the boundary is sufficiently heated to transfer, and the uniform transfer film 27 is formed. Can be obtained.

  FIG. 8B schematically shows a process in which the transfer layer 37 is heated and evaporated to be deposited on the support 21 of the device substrate 20 as the transfer film 27. At this time, the light irradiation can be stopped (the light irradiation of the portion is terminated by the movement of the light irradiation portion), and the light irradiation is continued as it is to transfer the entire right side portion of the transfer layer 37, and then The left part can also be transferred. In the first embodiment, if a material and light irradiation conditions are selected, an ablation mode in which the transfer layer 37 reaches the support 21 of the device substrate 20 with the film shape maintained can be used. However, from the viewpoint of reducing damage to the material, it is preferable to use a vapor deposition mode in which the transfer layer 37 evaporates in a state of being loosened by 1 to 100 molecules (atoms) and transferred.

  FIG. 8C shows one of the preferred modes of light irradiation in the first embodiment. Light that is wider than the width of the transfer layer 37 is applied to the entire width of the transfer layer 37 and a part of the width of the partition pattern 34. The light-to-heat conversion layer 33 is irradiated with light so that is simultaneously heated. According to this arrangement, the desired pattern of the transfer film 27 can be efficiently obtained by one transfer. Alternatively, the load on the transfer layer 37 can be further reduced by transferring half the film thickness of the transfer layer 37 by the first light irradiation and transferring the other half by the second light irradiation.

  The first embodiment is that the transfer layer 37 is divided and transferred multiple times in the film thickness direction by irradiating light to the photothermal conversion layer 33 multiple times on one donor substrate 30. This is a particularly preferable transfer method. As a result, not only the transfer layer 37 but also the partition pattern 34 and the underlying layer formed on the device substrate 20 can be reduced in maximum temperature, thereby preventing the donor substrate 30 from being damaged and the device substrate 20 from being degraded in performance. be able to. In the case of dividing, the number n is not limited. However, if the amount is too small, the above-mentioned effect under low temperature is not sufficiently exhibited. The range of is preferable.

  In the conventional method in which only the transfer material corresponding to one pixel is partially transferred, the effect of suppressing the material deterioration can be obtained even if the transfer is divided n times in the film thickness direction, but the processing per substrate is obtained. Since the time is approximately n times, productivity is greatly reduced. However, m (m is an integer of 2 or more) transfer materials can be transferred at once, so that productivity can be maintained. In particular, it is preferable to use wide light that satisfies the condition of m ≧ n because high productivity equal to or higher than that of the conventional method can be secured. In the production of displays, even a large substrate needs to be processed in about 2 minutes per sheet. Assuming that the laser scanning speed is 0.6 m / s as standard and one side of the substrate is 3 m, considering that 2 minutes are required for 24 scans (12 reciprocations), the number of divisions n is 15 times. The range of 30 times or more is particularly preferable.

  As shown in FIG. 6, when the donor substrate 30 has a plurality of transfer layers 37R, 37G, and 37B, it is not uncommon for the transfer layers 37R, 37G, and 37B to have different evaporation rate temperature characteristics. Therefore, when the donor substrate 30 as shown in FIG. 6 is irradiated with a wide uniform light as shown in FIG. 9 to be described later, for example, the transfer layer 37B has the entire film thickness by the first irradiation due to the difference in evaporation rate. Although transferred, only half the film thickness of 37R and 37G may be transferred. In this case, the remaining transfer of 37R and 37G can be completed by the second irradiation. At this time, the transfer layer 37B does not exist on the donor substrate 30 after the first irradiation, but the second irradiation can be performed in the same arrangement as the first irradiation. In the same way, for example, 37R can be transferred 10 times, 37G 7 times, 37B 5 times, and the like. It is also possible to use the donor substrate 30 in which the transfer layer 37B is not formed from the beginning and only the transfer layers 37R and 37G are formed.

  When the transfer layers 37R, 37G, and 37B are light emitting materials for organic EL elements, it is not uncommon for the transfer material to be a mixture of a host material and a dopant material, which have different evaporation rate temperature characteristics. For example, when the evaporation temperature of the dopant material is lower than that of the host material, a phenomenon in which all of the dopant material evaporates first when heated at a low temperature for a long time is likely to occur. On the other hand, a high temperature heating of a certain level or more makes it possible to use a phenomenon called flash evaporation in which the host material and the dopant material are evaporated at substantially the same ratio. In the present invention, since not only the light irradiation time and the light irradiation intensity but also the number of transfers can be controlled, it is relatively easy to find an appropriate high-speed evaporation condition according to flash evaporation while suppressing material deterioration. Therefore, it is possible to realize a transfer in which the ratio of the host material and the dopant material does not change before and after the transfer.

  Further, one donor substrate 30 is used such that about half of the thickness of the transfer layer 37 is transferred to one device substrate 20 by one light irradiation, and the other half is transferred to another device substrate 20. Transfer to the two device substrates 20 can also be performed. If the film thickness of the transfer material transferred to each device substrate 20 is adjusted, transfer from one donor substrate 30 to three or more device substrates 20 is also possible.

  Further, in the arrangement of light irradiation illustrated in FIG. 8C, the position of light irradiation is displaced in the x direction by δ as shown in FIG. 8D, and the entire width of the transfer layer 37 and the width of the partition pattern 34 are very small. Therefore, a uniform transfer film 27 can be obtained in the same manner.

  When the transfer layer 37 is formed of a precursor of the transfer material, the conversion process from the precursor to the original material is performed before the transfer process (Method I) or performed simultaneously with the transfer process (Method II). ) Is preferred. In the case of Method I, after applying the precursor compound on the donor substrate 30, conversion is performed by heat or light irradiation, and then transfer to the device substrate 20 is performed. In the case of Method II, after applying the precursor compound on the donor substrate 30, the donor substrate 30 and the device substrate 20 are overlapped and transferred to the device substrate 20, and this is performed by heating or light irradiation during the transfer. Transfer is performed while converting the precursor compound into a prototype material using energy. When transfer is performed with near-infrared laser light, laser light for transfer and light for conversion can be irradiated simultaneously. Among these, the method I is preferable because the conversion from the precursor material to the device material can be performed uniformly and at a high conversion rate.

  Next, a method for manufacturing a device using the donor substrate 30 in the first embodiment will be described. In this specification, a device refers to an organic EL element, an organic TFT, a photoelectric conversion element, various sensors, and the like. In the organic TFT, various electrodes such as an organic semiconductor layer, an insulating layer, a source, a drain, and a gate can be patterned, in an organic solar cell, an electrode and the like, and in a sensor, a sensing layer and an electrode can be patterned according to the present invention. Below, the organic EL element is mentioned as an example and the manufacturing method is demonstrated.

  9 and 10 are a cross-sectional view and a plan view showing an example of the thin film patterning method according to the first embodiment. In the drawings used in this specification, the minimum unit of RGB sub-pixels constituting a large number of pixels in a color display is extracted and described. In order to help understanding, the magnification in the vertical direction (substrate vertical direction) is increased as compared with the horizontal direction (substrate in-plane direction).

  In FIG. 9, the donor substrate 30 includes a support 31, a photothermal conversion layer 33, a partition pattern 34, and transfer layers 37 </ b> R, 37 </ b> G, and 37 </ b> B (coating films of RGB light emitting materials of organic EL) present in the partition pattern 34. Become.

  An organic EL element 10 which is an embodiment of the device includes a support 11, a TFT (including extraction electrode) 12 formed thereon, a planarization film 13, an insulating layer 14, a first electrode 15, and a hole transport layer 16. Become. In addition, since these are illustrations, the structure of each board | substrate is not limited to these as mentioned later.

  In a state where the partition pattern 34 of the donor substrate 30 and the insulating layer 14 of the device substrate 10 are aligned, the two substrates are arranged to face each other. A laser is incident from the support 31 side of the donor substrate 30 and absorbed by the light-to-heat conversion layer 33, and the transfer layers 37R, 37G, and 37B are simultaneously heated and evaporated by the heat generated in the light-to-heat conversion layer 33. The light emitting layers 17R, 17G, and 17B are collectively transferred and formed by depositing on the positive hole transport layer 16. Laser irradiation is performed so that the entire area of the partition pattern 34 sandwiched between the transfer layers 37R, 37G, and 37B and a part of the partition pattern 34 located outside the transfer layers 37R and 37B are heated simultaneously with the transfer layer 37. It is possible.

  Further, in the first embodiment, it is preferable that the thickness of the partition pattern 34 is larger than the thickness of the transfer layer 37. This is because when the partition pattern 34 is thicker than the transfer layer 37, the temperature of the thicker portion of the partition pattern 34 than the transfer layer 37 does not increase so much. This is because the partition pattern 34 is heated from the support 31 side, so that the upper part of the partition pattern 34 is difficult to warm because there is a distance from the heating source. Therefore, the organic EL element 10 is not heated to a high temperature through the partition pattern 34, there is almost no influence of degassing from the partition pattern 34, and the device performance is not deteriorated.

  Further, according to the first embodiment, different transfer layers 37R, 37G, and 37B that are separated by the partition pattern 34 can be heated by simultaneously irradiating light so as to straddle the partition pattern 34. Different transfer layers 37R, 37G, and 37B can be collectively transferred. Therefore, when the transfer layers 37R, 37G, and 37B of the organic EL element 10 are patterned according to the first embodiment, the transfer layers 37R, 37G, and 37B can be transferred together as a set, so that the transfer layer 37R, Patterning time can be shortened as compared with the conventional method in which it is necessary to sequentially irradiate light to 37G and 37B.

  Since the light is sufficiently absorbed by the photothermal conversion layer 33, the transfer layers 37R, 37G, and 37B having different light absorption spectra can be heated to the same temperature using the same light source, There is no concern that the EL element 10 is heated. The presence of the partition pattern 34 eliminates the transfer of adjacent adjacent transfer layers 37R, 37G, and 37B, and the transfer of the portion where the boundary position fluctuates. There is no.

  Further, since the partition pattern 34 can be patterned with high accuracy by a photolithography method or the like, a gap between transfer patterns of different transfer layers 37 can be minimized. This leads to the effect that the organic EL element 10 having a higher aperture ratio and excellent durability can be produced.

  FIG. 10 is a schematic view of the state of laser irradiation in FIG. 9 as viewed from the support 31 side of the donor substrate 30. Since the photothermal conversion layer 33 is formed on the entire surface, the partition pattern 34 and the transfer layers 37R, 37G, and 37B are not actually visible from the support 31 (glass plate) side, but the positional relationship with the laser will be described. Therefore, it is shown by a dotted line. The laser beam has a rectangular shape, is irradiated so as to straddle the transfer layers 37R, 37G, and 37B, and is scanned in a direction perpendicular to the arrangement of the transfer layers 37R, 37G, and 37B. The laser beam only needs to be scanned relatively, and the laser may be moved, the set of the donor substrate 30 and the device substrate 20 may be moved, or both.

  As often seen in display applications, when the set of transfer layers 37R, 37G, and 37B is repeatedly formed k times in the x direction and h times in the vertical y direction, for example, m sets (m By scanning light in the y direction while simultaneously irradiating light onto the transfer layers 37R, 37G, and 37B having a number of 2 to k, the transfer time can be reduced to about 1 / m.

  In the case of m = k, as shown in FIG. 11A, by irradiating light that covers the entire width of the transfer region 38 of the donor substrate 30, all transfer layers 37R, 37G, 37B can be batch-transferred. With this arrangement, alignment of light irradiation with respect to the donor substrate 30 can be greatly reduced. As shown in FIG. 11B, when there are a plurality of transfer regions 38 on the substrate, it is also possible to transfer them all at once. As is called a delta arrangement, even when the RGB sub-pixels are not arranged in a straight line, the irradiation light can be scanned in a straight line, so that the transfer can be easily performed.

  In the case of m <k, for example, as shown in FIG. 12A, light that covers about half the width of the transfer region 38 of the donor substrate 30 is irradiated, and the next scan is performed as shown in FIG. Then, the remaining half is irradiated with light, and all the transfer layers 37R, 37G, and 37B can be transferred in two scans (when m≈k / 2). Furthermore, as shown in FIG. 13, all the transfer layers 37R, 37G, and 37B can be transferred by simultaneously scanning two lights having different positional relationships in the scanning direction as in the above-described two scans. . Even if it is difficult to obtain a single light that covers the entire width of the transfer region 38 due to restrictions such as the maximum output of the light source and the uniformity of the light, a pseudo one-time scan (m = k) can be achieved by doing so. In the same manner, all the transfer layers 37R, 37G, and 37B can be collectively transferred. Of course, as shown in FIG. 14, the same effect can be obtained by further reducing the width of light and increasing the number.

  In the example of batch transfer described above, when the transfer layers 37R, 37G, and 37B have different evaporation temperatures (temperature dependence of vapor pressure), one light irradiation is performed according to the transfer material having the highest evaporation temperature. Batch transfer may be performed. On the other hand, for example, when the transfer layer 37R has the lowest evaporation temperature, the transfer layer 37R is entirely transferred by a single light irradiation, and 37G and 37B are partially transferred, and the light irradiation is repeated to 37G, The remainder of 37B may be transferred, or may be divided into three or more transfers. Since the transfer time can be shortened to about 1 / m, the damage to the transfer layer 37 can be further reduced by dividing the transfer time into m times over the same time. The optimum one can be selected from various transfer conditions while taking into consideration the time available for the transfer process and the damage to the transfer material.

  As described above, the great effect of the batch transfer is that it is not necessary to control the light irradiation position as precisely as in the conventional method. For example, when light is emitted from a light source placed in the atmosphere to a donor substrate 30 placed in a vacuum, the conventional method cannot neglect a minute optical path change caused by a transparent window that separates the atmosphere and the vacuum. There is a problem that it is necessary to put all the light source and the light scanning mechanism in a vacuum, which imposes a large burden on the apparatus. On the other hand, in the method of the present invention, the above optical path change can be ignored, so that not only the light irradiation apparatus but also the entire mechanism of the transfer process apparatus can be simplified.

  The batch transfer has another effect. In the wide light irradiation range, the lateral thermal diffusion that has become a problem in laser transfer does not occur, so it is possible to irradiate light for a relatively long time, such as by scanning the laser at a relatively low speed. It becomes possible. Therefore, the maximum temperature of the transfer material can be controlled more easily, and high-precision patterning can be performed without damaging the transfer material during transfer, so that deterioration in device performance can be minimized. Further, when the damage to the transfer material is reduced, the damage to the partition pattern 34 is also reduced at the same time, so that the partition pattern 34 is hardly deteriorated. Therefore, the donor substrate 30 can be reused a plurality of times, and the cost for patterning can be reduced.

  The scanning speed of the laser is not particularly limited, but a range of 0.01 to 2 m / s is generally preferably used. When the light irradiation intensity is relatively small and the damage to the transfer material is reduced by scanning at a lower speed, the scanning speed is preferably 0.6 m / s or less, more preferably 0.3 m / s or less. . When the overall temperature is lowered by increasing the number of divisions as in the above-described divided transfer, the scan speed is relatively high, 0.3 m / s or more in order to reduce the amount of input heat per scan. It is preferable that

  As a light source of irradiation light, a laser that can easily obtain high intensity and excellent in shape control of irradiation light can be exemplified as a preferable light source. However, a light source such as an infrared lamp, a tungsten lamp, a halogen lamp, a xenon lamp, or a flash lamp is used. You can also As the laser, a known laser such as a semiconductor laser, a fiber laser, a YAG laser, an argon ion laser, a nitrogen laser, or an excimer laser can be used. Since one of the objects in the present invention is to reduce damage to the transfer material, the continuous wave mode (CW) laser is more suitable than the intermittent oscillation mode (pulse) laser irradiated with high intensity light in a short time. Is preferred.

  The wavelength of the irradiation light is not particularly limited as long as absorption in the irradiation atmosphere and the support 31 of the donor substrate 30 is small and the light-to-heat conversion layer 33 is efficiently absorbed. Therefore, not only visible light region but also ultraviolet light to infrared light can be used. Considering a suitable material for the support 31 of the donor substrate 30, 300 nm to 5 μm can be exemplified as a preferable wavelength region, and 380 nm to 2 μm can be illustrated as a more preferable wavelength region.

The shape of irradiation light is not limited to the rectangle illustrated above. The optimum shape can be selected according to the transfer conditions such as linear, elliptical, square, polygonal. Irradiation light may be formed by superposition from a plurality of light sources, or conversely, a single light source may be divided into a plurality of irradiation lights.
The preferable ranges of irradiation intensity and heating temperature of the transfer material are uniformity of irradiation light, irradiation time (scanning speed), material and thickness of the support 31 and the photothermal conversion layer 33 of the donor substrate 30, reflectivity, and partition pattern 34. It is influenced by various conditions such as the material and shape of the transfer material and the material and thickness of the transfer material. In the present invention, the energy density absorbed by the light-to-heat conversion layer 33 is in the range of 0.01 to 10 J / cm ² , and the irradiation conditions are adjusted so that the transfer layer 37 is heated to the range of 220 to 400 ° C. It becomes.

  In Embodiment 1 of the present invention, by forming a partition pattern from the above siloxane composition, the linearity and smoothness of the partition pattern is improved by patterning by a photolithographic method, and the adhesion to the photothermal conversion layer is improved. Since it becomes high, it becomes possible to improve the durability of the donor substrate.

(Embodiment 2)
The second embodiment of the present invention differs from the first embodiment in that the donor substrate 30 has a barrier layer 36. Hereinafter, the donor substrate 30 according to the second embodiment will be described with reference to FIGS. 15 and 16.

  As shown in FIG. 15A, the barrier layer 36 is formed on the partition pattern 34. In the donor substrate 30, laser light or the like is incident on the photothermal conversion layer 33 from the support 31 side, and the light incident on the photothermal conversion layer 33 is converted into heat to transfer the transfer layer 37 to the device substrate 20 or the like. The heat generated by the photothermal conversion layer 33 is also transmitted to the partition pattern 34, but the thickness of the partition pattern 34 does not affect the heat conduction from the partition pattern 34 to the device substrate 20. However, degassing and decomposition products may occur in the partition pattern 34 due to the thermal history due to the transfer process. For this reason, when the donor substrate 30 is used repeatedly, degassed or decomposed products generated in the solvent in which the transfer material is dissolved are eluted from the interface between the photothermal conversion layer 33 and the partition pattern 34 and transferred to the device substrate 20 together with the transfer material. As a result, the performance of the device substrate 20 may be deteriorated. In the donor substrate 30 of the second embodiment, by providing the barrier layer 36 on the partition pattern 34, it is possible to prevent elution of decomposition products or the like from the partition pattern 34 to the transfer layer 37. Furthermore, by using a siloxane composition as the material of the partition pattern 34, the adhesion between the partition pattern 34 and the barrier layer 36 is improved, and the effect of improving the durability of the donor substrate 30 can be obtained.

  Examples of the material for forming the barrier layer 36 include metals, metal oxides, metal nitrides, silicon oxides, and silicon nitrides. Since the donor substrate 30 is often repeatedly cleaned and reused, durability is required so that the film does not peel off. Therefore, a material having high adhesion to the photothermal conversion layer 33 and the partition pattern 34 should be selected. Is preferred. Of these, metals, such as chromium, nickel, zinc, titanium, vanadium, tantalum, and manganese, are preferable in terms of adhesion. Furthermore, the same kind of metal as the photothermal conversion layer 33 is more preferable because the adhesion to the photothermal conversion layer 33 is improved. In addition, the following reasons can be given for the point that a metal is preferable as the barrier layer 36. Since the metal has a high density and a high covering property, the elution of low molecular components from the partition pattern can be greatly suppressed. Moreover, since it can extend with respect to plastic deformation, it is hard to generate | occur | produce a crack with respect to a thermal stress, and there exists a big advantage at the point of impurity elution.

  It is also possible to provide a plurality of barrier layers 36. In this case, the above materials can be freely combined for each layer. Among these, it is more preferable to provide an adhesion layer in a portion in contact with the partition pattern 34 and the photothermal conversion layer 33 and to provide a material having good weather resistance on the outermost surface. The adhesion layer preferably contains any of chromium, nickel, zinc, titanium, vanadium, tantalum, and manganese, and the surface may be slightly oxidized or nitrided. The outermost layer consists of chemically stable noble metals such as gold, silver, platinum, palladium, rhodium, iridium, ruthenium, osmium, metal oxides, silicon oxides, silicon nitrides, and metals with excellent acid resistance. It is desirable that a layer is formed. Examples of metals excellent in acid resistance include vanadium, niobium, tantalum, titanium, zircon, hafnium / tungsten, and the like. When silicon oxide is used for the outermost surface, the material itself has a high barrier property, but the silicon oxide itself tends to be porous, and in this case, the surface area increases and, on the contrary, it becomes easy to absorb moisture. Accompanying this, the surface residual amount of ionic impurities such as chlorine during cleaning and fluorine or the like during liquid repellency treatment increases, and the performance of the device to which it is transferred may be reduced. For this reason, it is desirable to provide an outermost surface layer such as a metal, particularly a noble metal, because a smooth surface state is easily formed.

  The method for producing the barrier layer 36 is not particularly limited, but generally, a sputtering method, a vapor deposition method, a CVD method, or the like can be considered. The thickness is not particularly limited, but is preferably 0.05 μm or more from the viewpoint of durability. In the case of FIG. 15A in which the barrier layer 36 is also formed in the partition pattern 34 (inside the cell), from the viewpoint of efficiently conducting heat from the photothermal conversion layer 33 to the transfer material via the barrier layer 36, the barrier layer 36 is formed. The thickness of the layer 36 is preferably 0.7 μm or less, and more preferably 0.5 μm or less. In the case of FIG. 15B in which the barrier layer is formed only on the partition pattern 34, the barrier layer 36 can be made thicker and the durability can be improved. In addition, a manufacturing method in the case where the barrier layer 36 is formed only on the partition pattern 34 is not particularly limited, but as an example, only on the partition pattern by a vacuum deposition method or a sputtering method using a mask opened only on the partition pattern 34. There is a method of forming a barrier layer. Further, a barrier layer 36 is formed on the entire surface of the partition pattern 34, and thereafter a resist is formed by photolithography so that portions other than the partition pattern 34 are exposed, and the opening is etched to form the barrier layer 36 only on the partition pattern 34. It can also be formed. Since the barrier layer 36 only needs to cover at least the partition pattern 34, when the barrier layer 36 is also formed in the partition pattern 34, it may be formed only on a part thereof.

As shown in FIG. 16, a liquid repellent treatment layer 35 is provided on the surface of the barrier layer 36 on the partition pattern 34 to retain the solution in which the transfer material is dissolved in the partition pattern 34. preferable.
Moreover, since the barrier layer 36 is formed using the same material as the photothermal conversion layer 33, in addition to the function as the barrier layer 36, the barrier layer 36 may have a function as the photothermal conversion layer 33. In the case where the barrier layer 36 also functions as a photothermal conversion layer, it is not necessary to provide the photothermal conversion layer 33 on the support 31 as shown in FIG. However, since light is also incident on the barrier layer 36 in contact with the device substrate 20 via the partition pattern 34, the heat is directly conducted from the barrier layer 36 to the device substrate 20, so that the influence of heating of the device substrate 20 is increased. . Therefore, when the barrier layer 36 performs photothermal conversion without providing the photothermal conversion layer 33, it is preferable to provide a reflective layer 39 or the like below the partition pattern 34 as shown in FIG.

  After the partition pattern 34 and the barrier layer 36 are formed as described above, the transfer material 37 is stacked in the partition pattern 34 to form the transfer layer 37 in the same manner as in the first embodiment. The donor substrate 30 concerning this can be produced.

  The donor substrate according to the second embodiment is excellent in the linearity and smoothness of the partition pattern, and can prevent the elution of impurities to the transfer layer by the barrier layer, so that a device substrate having better device performance is manufactured. be able to.

The donor substrate 30 was produced as follows. Using a non-alkali glass substrate (surface Ra: 3 nm) of 38 × 46 mm and a thickness of 0.7 mm as the support 31, the support 31 is etched with hydrofluoric acid, and the surface on the side where the photothermal conversion layer is formed is roughened (Surface Ra: 30 nm). Ra of the surface of the support 31 was 30 nm. After cleaning / UV ozone treatment, a tantalum film having a thickness of 0.2 μm was formed as a photothermal conversion layer 33 by sputtering (gas type: Ar, gas pressure: 0.2 Pa, power: 1 kW). Ra of the photothermal conversion layer 33 was also 30 nm. After the photothermal conversion layer 33 is subjected to UV ozone treatment, a positive photosensitive siloxane composition containing a siloxane polymer (A) represented by the following formula (5) is spin-coated, and then heated at 90 ° C. for 3 minutes using a hot plate. Pre-baked. The siloxane polymer of the formula (5) is obtained by mixing and reacting methyltrimethoxysilane and phenyltrimethoxysilane in a molar ratio of 65:35. The prepared film was exposed at 300 mJ / cm ² through a gray scale mask for sensitivity measurement using PLA (PLA-501F manufactured by Canon Inc.) through a gray scale mask for sensitivity measurement, and then 2.38% tetramethyl hydroxide. Shower-developed with an aqueous ammonium solution for 90 seconds and then rinsed with water for 30 seconds. Thereafter, as a bleaching exposure, a parallel light mask aligner (PLA) (PLA-501F manufactured by Canon Inc.) was used, and the entire surface of the film was exposed to 1000 mJ / cm ² of an ultrahigh pressure mercury lamp, and at 90 ° C. using a hot plate. After heating for 2 minutes, it was cured in an oven at 230 ° C. for 1 hour to form a partition pattern 34. Next, a barrier layer 36 made of a tantalum film having a thickness of 0.2 μm was formed on the entire surface of the donor substrate 30 by sputtering, and a fluorine-based liquid repellent treatment was performed on the upper surface of the partition pattern 34. The partition pattern 34 had a thickness of 10 μm, a width of 20 μm, and a cross section of a forward tapered shape. Inside the partition pattern 34, openings having a width of 80 μm and a length of 280 μm were arranged at a pitch of 100 μm in the width direction and 300 μm in the length direction.

  The transfer donor substrate and the device substrate manufacturing method according to the present invention are useful for patterning thin films constituting devices such as organic TFTs, photoelectric conversion elements, and various sensors including organic EL elements, and are used for cellular phones and personal computers. It can be used for manufacturing display panels, touch panels, imaging devices, etc. used in televisions, image scanners, and the like.

10 Organic EL elements (device substrates)
11 Support 12 TFT (including extraction electrode)
DESCRIPTION OF SYMBOLS 13 Flattening film 14 Insulating layer 15 1st electrode 16 Hole transport layer 17 Light emitting layer 20 Device substrate 21 Support body 27 Transfer film 30 Donor substrate 31 Support body 33 Photothermal conversion layer 34 Partition pattern 35 Liquid repellent treatment layer 36 Barrier layer 37 Transfer layer 38 Transfer area 39 Reflective layer

Claims (8)

A donor substrate for transfer having a support, a light-to-heat conversion layer that absorbs light to generate heat, and a partition pattern that partitions the transfer layer;
The partition pattern is formed of a siloxane composition containing a siloxane polymer (A) obtained by reacting at least one siloxane compound represented by the following general formula (1).
(In General Formula (1), R ¹ is hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 16 carbon atoms, and R ² is hydrogen or carbon. An alkyl group having 1 to 10 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms, n is an integer of 0 to ^{3. When a} plurality of R ¹ and R ² are present, May be the same or different.)   2. The donor substrate for transfer according to claim 1, wherein the surface of the photothermal conversion layer is a rough surface.   The donor substrate for transfer according to claim 1, wherein the surface of the light-to-heat conversion layer has an arithmetic average roughness of 30 nm or more.   The donor substrate for transfer according to any one of claims 1 to 3, wherein the arithmetic average roughness of the surface of the support on the side where the photothermal conversion layer is formed is 30 nm or more.   The said photothermal conversion layer is formed on the said support body, The barrier layer was formed in the division pattern surface formed in the upper surface of this photothermal conversion layer, It is any one of Claims 1-4 characterized by the above-mentioned. Donor substrate for transfer.   The transfer donor substrate according to claim 1, further comprising a liquid repellent treatment layer formed at least on the partition pattern. The siloxane polymer (A) is a photosensitive polymer having a phenolic hydroxyl group content of 0.2 mol or less per 1 mol of Si atoms,
In addition to the siloxane polymer (A), the siloxane composition includes:
A naphthoquinone diazide sulfonic acid ester of a compound having a phenolic hydroxyl group, wherein the ortho position and the para position of the phenolic hydroxyl group are each independently hydrogen or a quinonediazide having a substituent represented by the following general formula (2) Compound (B),
The donor substrate for transfer according to claim 1, comprising a compound having an alcoholic hydroxyl group and / or a cyclic compound (C) having a carbonyl group.
(In General Formula (2), R ³ , R ⁴ , and R ⁵ are each independently an alkyl group having 1 to 10 carbon atoms, a carboxyl group, or an optionally substituted phenyl group. , R ³ , R ⁴ and R ⁵ may combine to form a ring.) An alignment step of aligning the partition pattern provided in the donor substrate for transfer according to any one of claims 1 to 7 with the insulating layer of the device substrate facing each other,
A transfer step of irradiating the photothermal conversion layer of the donor substrate for transfer with light to transfer the transfer layer to the device substrate;
A method for manufacturing a device substrate, comprising: