CN111999979A

CN111999979A - Method for manufacturing non-photoetching patterned mask

Info

Publication number: CN111999979A
Application number: CN202010758022.XA
Authority: CN
Inventors: 李中天; 姚宇; 邓晓帆
Original assignee: Suzhou Taiyangjing New Energy Co ltd
Current assignee: Suzhou Taiyangjing New Energy Co ltd
Priority date: 2020-07-31
Filing date: 2020-07-31
Publication date: 2020-11-27

Abstract

The invention provides a method for manufacturing a non-photoetching patterned mask, which comprises the following steps: s1, arranging a layer of high polymer material on a substrate; s2, contacting a part of regions which are not required to be reserved in the layer of high molecular material with a solution containing a polymerization inhibitor or a retarder; s3, carrying out heat treatment on the substrate containing the high polymer material; and S4, soaking the substrate containing the high polymer material in a developing solution or developing by a spray developing method until the region of the high polymer material contacting with a polymerization inhibitor or a retarder is dissolved. Compared with the traditional photoetching process or dry film process, the method for patterning the mask does not need a light source and an exposure process, and does not need to add a photosensitive component in a high polymer material, so that the material cost is greatly reduced, and the method is applied to the application field needing the low-cost mask.

Description

Method for manufacturing non-photoetching patterned mask

Technical Field

The invention relates to the field of micron-scale manufacturing of solar cells, semiconductor lighting chip manufacturing, flat panel display, biochemical analysis chips, integrated circuits, micro-electro-mechanical manufacturing and the like, in particular to a manufacturing method of a patterned mask.

Background

The photolithography process is an essential process in the process of manufacturing the thin film transistor array, and plays a role in pattern transfer. The designed mask pattern is transferred to the film by cleaning, photoresist coating, exposure, development, post-baking and other processes, and then a target pattern is formed in the film through etching and photoresist stripping processes.

The main component of the photoresist is a polymer containing photosensitive groups, and the photosensitive groups of the photoresist are chemically changed under the condition of ultraviolet illumination, so that the solubility of the photosensitive parts and the light-shielding parts of the photoresist in a developing solution is different, and the pattern transfer is realized after the development.

The cost of photomask and photoresist materials does not meet the low cost requirements of the solar cell industry. And moreover, the time required by exposure and development of the photoresist can not meet the yield requirement of the modern solar cell production line by aligning the photomask. The patterning process may be used in different steps in the solar cell manufacturing process. For example, when a conductive grid line is selectively deposited on the surface of a solar cell, a patterning process may be required to complete the process. Patterning processes are also required in many other applications, such as depositing protective coatings on glass substrates, forming conductive patterns on circuit boards, and the like.

These applications do not generally require the high resolution and precise alignment advantages that are exerted by photolithographic techniques in microelectronics industry applications. Therefore, there is a need for a method of patterning high molecular weight polymers that is higher throughput and lower cost than conventional photolithography.

Disclosure of Invention

The technical problem to be solved is as follows: the object of the present invention is to provide a method for producing a non-lithographic patterned mask, which can efficiently crosslink a polymer resin by using a polymerization inhibitor and can obtain a patterned mask at a high efficiency and a low cost.

The technical scheme is as follows: a method of making a non-lithographically patterned mask, comprising the steps of:

s1, arranging a layer of high polymer material on a substrate;

s2, contacting a part of regions which are not required to be reserved in the layer of high molecular material with a solution containing a polymerization inhibitor or a retarder;

s3, carrying out heat treatment on the substrate containing the high polymer material;

and S4, soaking the substrate containing the high polymer material in a developing solution or developing by a spray developing method until the region of the high polymer material contacting with a polymerization inhibitor or a retarder is dissolved.

Preferably, the polymer material in step S1 is composed of the following components in parts by weight:

high molecular resin: 2% -60%;

curing agent: 0% -25%;

other auxiliary agents: 0 to 5 percent;

solvent: and (4) the balance.

high molecular resin: 15% -40%;

curing agent: 0% -10%;

other auxiliary agents: 0 to 2 percent;

solvent: and (4) the balance.

Preferably, the polymer resin contains active hydrogen bonds including hydroxyl, carboxyl or amide groups; including alkyd resins, polyester resins, novolac resins, acrylic resins, epoxy resins, polyimides, urethanes, polyvinylphenols, polyacrylic acids or polymethacrylic acid copolymers; preferred are poly-p-hydroxystyrene resin, epoxy resin, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid copolymer or a mixture thereof;

the solvent is a good solvent of a high polymer material; glycol ethers including aromatic hydrocarbons, alcohols, ethers, esters, ketoamides or chlorinated hydrocarbons, preferably ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, triethylene glycol butyl ether; esters of ethyl acetate, 1, 2-propylene glycol methyl ether acetate, butyl acetate, ethyl lactate, isobutyl isobutyrate, 1, 4-butyrolactone, ethylene glycol monoacetate, ethylene glycol methyl ether acetate, ethylene glycol alkyl ether acetate, propylene glycol methyl ether acetate, ethyl 3-ethoxypropionate, ethoxyethyl acetate; cellosolve acetate, cellosolve esters of ethyl cellosolve acetate; toluene, aromatic hydrocarbons of xylene; ketones of acetone, butanone, cyclopentanone, cyclohexanone; amides of dimethylacetamide, N-methylpyrrolidone, dimethylformamide; chlorinated hydrocarbons of dichloromethane, dichloroethane, 1,1, 1-trichloroethane, chlorobenzene, o-dichlorobenzene; and mixtures of the foregoing;

the curing agent is chemically reacted with a high molecular material to form a reticular three-dimensional polymer; preferably heterocyclic compounds containing ether bonds; the ether bond is linked into a C-hydrocarbon chain with 6 carbon atoms and/or a halogen-containing hydrocarbon and/or a benzene ring and a benzene ring derivative, and the ether bond and the film-forming polymer resin are subjected to a crosslinking reaction; or the curing agent can perform condensation reaction with the phenolic hydroxyl or the ortho/para hydroxymethyl functional group in the polymer resin to form a methine bond and a small amount of ether bond, so that the polymer resin forms a reticular cross-linked structure; preferably vinyl triamine, diaminocyclohexane, melamine, dihexyl triamine or mixtures thereof;

the other auxiliary agents comprise a tackifier, or/and a dispersion stabilizer, or/and a defoaming agent, or/and a surfactant, or/and an antioxidant.

Preferably, the solution of the polymerization inhibitor or retarder in the step S2 is composed of the following components in parts by weight:

polymerization inhibitor or retarder: 0.1% -50%;

other stabilizers: 0% -10%;

solvent: and (4) the balance.

polymerization inhibitor or retarder: 0.5% -10%;

other stabilizers: 1% -5%;

solvent: and (4) the balance.

Preferably, the polymerization inhibitor or retarder comprises an addition type polymerization inhibitor, a chain transfer type polymerization inhibitor and a charge transfer type polymerization inhibitor, the addition type polymerization inhibitor comprises quinones, nitro compounds, oxygen-containing compounds and sulfur-containing compounds, the quinones comprise benzoquinone, hydroquinone (hydroquinone), 2, 5-di-tert-butylhydroquinone, naphthoquinone and hydroquinone monomethyl ether, the nitro compounds comprise nitrobenzene, 1-methyl-3-nitrobenzene and polynitrobenzene, 2-sec-butyl-4, 6-dinitrophenol, the oxygen-containing compounds comprise 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxygen radical, and the sulfur-containing compounds comprise copper sulfide; the chain transfer polymerization inhibitor comprises 1, 1-diphenyl-2-trinitrophenylhydrazine, aromatic amine and phenols, wherein the aromatic amine comprises phenothiazine, N-methyl-N-nitrosoaniline and N-phenyl naphthylamine, and the phenols comprise resorcinol, 2, 6-di-tert-butyl-p-cresol and p-tert-butyl catechol; the charge transfer polymerization inhibitor comprises ferric chloride, copper chloride and a mixture of the ferric chloride and the copper chloride;

the stabilizer comprises a dispersion stabilizer, a humectant, a pH regulator, a defoaming agent, a chelating agent and a surfactant.

Preferably, the heat treatment in step S3 includes treatment with a heating plate, a heating furnace, an infrared heating device and a microwave heating device, the surface temperature of the substrate is 60-160 ℃, and the time is controlled within 10S-20 min.

Preferably, the developing in step S4 is performed in TMAH or alkaline developer (PH >9) for 20S-10min at 20-50C.

Has the advantages that: the manufacturing method of the invention has the following advantages:

1. the polymerization inhibitor prevents the polymerization of the high polymer material, after the high polymer material is cured, the high polymer material containing the polymerization inhibitor is not cured, and the high polymer material containing the polymerization inhibitor is dissolved under the action of a developing solution, so that a pattern is formed;

2. compared with the traditional photoetching process or dry film process, the method for patterning the mask does not need a light source and an exposure process, and does not need to add a photosensitive component in a high polymer material, so that the material cost is greatly reduced, and the total cost of the process can be reduced in the application fields needing low-cost masks, such as PCB (printed circuit board) manufacturing, photovoltaic cell manufacturing, semiconductor lighting chip manufacturing, flat panel display and the like; 3. The method for realizing the graphical mask by the non-photoetching process simplifies the photoetching procedures of prebaking, exposing, developing and the like in the traditional photoetching process, and realizes a faster, simpler and more effective graphical preparation way;

4. compared with the patterning mask process in the prior art, the method has the advantages that the opening edge is clear, a large amount of solution does not need to be provided on the high polymer material layer, the opening is finer, and the method has the advantages of high efficiency, rapidness, high conversion rate and controllable product structure in practical application;

5. in conclusion, the invention has the advantages of cost and performance, can form a high-precision low-cost graphical mask in a micrometer scale, and is expected to be applied in multiple fields.

Drawings

FIG. 1 shows a device opening structure formed on a polymer material layer by the method of the present invention

FIG. 2 is a schematic view of a dot-shaped opening formed in a polymer material layer by the method of the present invention;

fig. 3 is a diagram of a polymer material layer manufactured by the method of the present invention.

Detailed Description

The method for manufacturing a non-lithographic patterned mask according to the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments. Advantages and features of the present invention will become apparent from the following description and from the claims. It is to be noted that the drawings are in a very simplified form and are not to precise scale, which is merely for the purpose of facilitating and distinctly claiming the embodiments of the present invention.

In view of the problems of high cost and complicated steps compared with the photoetching process or dry film process in the prior art, the invention provides the manufacturing method of the non-photoetching patterned mask, which has the advantages of high efficiency, rapidness, high conversion rate and controllable product structure. The specific manufacturing method of the non-photoetching patterned mask comprises the following steps:

s1, arranging a layer of high polymer material on a substrate;

high molecular resin: 2% -60%;

curing agent: 0% -25%;

other auxiliary agents: 0 to 5 percent;

solvent: and (4) the balance.

high molecular resin: 15% -40%;

curing agent: 0% -10%;

other auxiliary agents: 0 to 2 percent;

solvent: and (4) the balance.

the other auxiliary agents include a tackifier, a dispersion stabilizer or a defoaming agent.

polymerization inhibitor or retarder: 0.1% -50%;

other stabilizers: 0% -10%;

solvent: and (4) the balance.

polymerization inhibitor or retarder: 0.5% -10%;

other stabilizers: 1% -5%;

solvent: and (4) the balance.

Preferably, the heat treatment comprises treatment of a heating plate, a heating furnace, infrared heating equipment and microwave heating equipment, the surface temperature of the substrate is 60-160 ℃, and the time is controlled within 10 s-20 min.

For further understanding of the present invention, the following examples are given to illustrate the preparation method of the present invention, and the scope of the present invention is not limited by the following examples.

Example 1

S1, coating a polymer material solution containing 20 wt% of triethylene glycol diacrylate, 5 wt% of a vinyl triamine curing agent and 75 wt% of a glycol monoethyl ether solvent on the surface of a glass substrate by a roller coating method;

s2, locally printing a solution containing 22 wt% of 1, 1-diphenyl-2-trinitrophenylhydrazine serving as a polymerization inhibitor by using an ink-jet printing method after preparing the substrate containing the high polymer material;

s3, heating the substrate prepared in the step S2 to 100 ℃, and maintaining for 1 minute;

s4, cooling the heated substrate, and then placing the substrate in a potassium hydroxide developing solution with the concentration of 3 wt% for developing for 3 minutes, wherein the triethylene glycol diacrylate layer can be dissolved by the developing solution in a printing area.

Example 2

S1, coating a high polymer material solution containing 18 wt% of pentaerythritol triacrylate, 4 wt% of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane curing agent and 78 wt% of 1, 2-propylene glycol methyl ether acetate solvent on the surface of a silicon wafer substrate in a screen printing mode;

s2, locally spraying a solution containing 2 wt% of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxygen radical serving as a polymerization inhibitor by using a spraying method after the substrate containing the high polymer material is prepared in the step;

s3, heating the substrate prepared in the step S2 to 90 ℃, and maintaining for 5 minutes;

s4, cooling the heated substrate, and then placing the substrate in a sodium hydroxide developing solution with the concentration of 2 wt% for developing for 1 minute, wherein the pentaerythritol triacrylate layer can be dissolved by the developing solution in a printing area.

Example 3

S1, coating a high polymer material solution containing 25 wt% of unsaturated acrylic polyester and 75 wt% of benzil dimethyl ketal as a solvent on the surface of a glass substrate by a spin coating method (wherein the rotating speed is 3000rpm, and the time is 1 min);

s2, partially printing a polymerization inhibitor solution containing 10 wt% of 1, 1-diphenyl-2-trinitrophenylhydrazine through an aerosol printing method after preparing the substrate containing the high polymer material;

s3, heating the substrate prepared in the step S2 to 130 ℃, and maintaining for 3 minutes;

and S4, cooling the heated substrate, and then placing the substrate in TMAH developing solution with the concentration of 5 wt% for developing for 2 minutes, wherein the unsaturated acrylic polyester layer can be dissolved by the developing solution in the printing area.

Example 4

S1, coating a high polymer material solution containing 20 wt% of bisphenol A type novolac epoxy resin and 80 wt% of 1, 4-butyrolactone solvent on the surface of a glass substrate by a roller coating method;

s2, locally printing a solution containing 3 wt% of ferric chloride serving as a polymerization inhibitor by using the substrate containing the high polymer material prepared in the step through an ink-jet printing method;

s3, microwave heating the substrate prepared in the step S2 to 160 ℃, and maintaining for 5 minutes;

and S4, cooling the heated substrate, and then placing the substrate in a polyimide developing solution for developing for 8 minutes, wherein the bisphenol A type novolac epoxy resin layer can be dissolved by the developing solution in a printing area.

Example 5

S1, coating a high polymer material solution containing 15 wt% of poly (p-hydroxystyrene) resin, 15 wt% of dihexyl triamine and 70 wt% of 1, 2-propylene glycol methyl ether acetate solvent on the surface of a glass substrate by a spin coating method (wherein the rotating speed is 3000rpm and the time is 1 min);

s2, locally printing a solution containing 3 wt% of copper sulfide serving as a polymerization inhibitor by using the substrate containing the high polymer material prepared in the step through an ink-jet printing method;

s3, microwave heating the substrate prepared in the step S2 to 110 ℃, and maintaining for 1 minute;

s4, cooling the heated substrate, and then placing the substrate in a 3% TMAH developing solution for developing for 8 minutes, wherein the poly-p-hydroxystyrene resin layer can be dissolved by the developing solution in a printing area.

Example 6

S1, coating a high polymer material solution containing 8 wt% of a mixture of poly-p-hydroxystyrene resin and epoxy resin, 5 wt% of melamine, 87% of a mixed solvent of 1, 2-propylene glycol methyl ether acetate and butanone (the mass ratio of the solvent is 1: 1) on the surface of a glass substrate by a spin coating method (wherein the rotating speed is 3000rpm, and the time is 1 min);

s2, locally printing a solution containing 5 wt% of benzoquinone serving as a polymerization inhibitor by using the substrate containing the high polymer material prepared in the step through an ink-jet printing method;

s3, keeping the temperature in the substrate baking oven prepared in the step S2 to 60 ℃ for 10 minutes;

Example 7

S1, coating a polymer material solution containing 20 wt% of alkyd resin and 80% of ethylene glycol monoethyl ether solvent on the surface of a glass substrate by a roller coating method;

s2, locally printing a solution containing 5 wt% of nitrobenzene serving as a polymerization inhibitor by using an ink-jet printing method after the substrate containing the high polymer material is prepared in the step;

s3, heating the substrate prepared in the step S2 to 60 ℃, and maintaining for 10 minutes;

s4, cooling the heated substrate, and then placing the substrate in a potassium hydroxide developing solution with the concentration of 3 wt% for developing for 3 minutes, wherein the alkyd resin layer can be dissolved by the developing solution in the printing area.

Example 8

S1, coating a polymer material solution containing 30 wt% of poly (p-hydroxystyrene) resin, 5 wt% of a vinyl triamine curing agent and 65 wt% of a ethylene glycol monoethyl ether solvent on the surface of a glass substrate by a roller coating method;

s2, locally printing a solution which contains 0.1 wt% of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxygen radical serving as a polymerization inhibitor by using an ink-jet printing method after preparing the substrate containing the high polymer material;

s3, heating the substrate prepared in the step S2 to 100 ℃, and maintaining for 2 minutes;

s4, cooling the heated substrate, and then placing the substrate in a potassium hydroxide developing solution with the concentration of 3 wt% for developing for 3 minutes, wherein the poly-p-hydroxystyrene resin layer can be dissolved by the developing solution in the printing area.

Example 9

s2, locally printing a solution containing 1 wt% of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxygen radical serving as a polymerization inhibitor by using an ink-jet printing method after preparing the substrate containing the high polymer material;

Example 10

s2, locally printing a solution containing 10 wt% of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxygen radical serving as a polymerization inhibitor by using an ink-jet printing method after preparing the substrate containing the high polymer material;

Example 11

s2, locally printing a solution containing 30 wt% of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxygen radical serving as a polymerization inhibitor by using an ink-jet printing method after preparing the substrate containing the high polymer material;

Comparative example 1

s2, locally printing a solution containing 60 wt% of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxygen radical serving as a polymerization inhibitor by using an ink-jet printing method after preparing the substrate containing the high polymer material;

Comparative example 2

s2, locally printing a solution which contains 0.05 wt% of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxygen radical serving as a polymerization inhibitor by using an ink-jet printing method after preparing the substrate containing the high polymer material;

Examples 8-11, and comparative examples 1 and 2, the process parameters were the same except for the polymerization inhibitor content, and the results are shown in the following table:

as can be seen from the above table, by contacting a part of the unnecessary remaining region of the layer of the high-molecular material with a solution containing a polymerization inhibitor or a retarder, the contacted part can be completely dissolved within a reasonable range.

The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method of making a non-lithographic patterned mask, comprising the steps of:

s1, arranging a layer of high polymer material on a substrate;

2. The manufacturing method according to claim 1, wherein the polymer material in the step S1 is composed of the following components in parts by weight:

high molecular resin: 2% -60%;

curing agent: 0% -25%;

other auxiliary agents: 0 to 5 percent;

solvent: and (4) the balance.

3. The manufacturing method according to claim 2, wherein the polymer material in the step S1 is composed of the following components in parts by weight:

high molecular resin: 15% -40%;

curing agent: 0% -10%;

other auxiliary agents: 0 to 2 percent;

solvent: and (4) the balance.

4. The method of claim 3, wherein the polymeric resin contains active hydrogen bonds including hydroxyl, carboxyl, or amide groups; including alkyd resins, polyester resins, novolac resins, acrylic resins, epoxy resins, polyimides, urethanes, polyvinylphenols, polyacrylic acids or polymethacrylic acid copolymers; preferred are poly-p-hydroxystyrene resin, epoxy resin, polyvinylpyrrolidone, phenol resin, polyacrylic acid, polymethacrylic acid copolymer or a mixture thereof;

the solvent is a good solvent of a high polymer material; organic solvents including aromatic hydrocarbons, alcohols, ethers, esters, ketoamides or chlorinated hydrocarbons, preferably glycol ethers of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, triethylene glycol butyl ether, or propylene glycol methyl ether; esters of ethyl acetate, 1, 2-propylene glycol methyl ether acetate, butyl acetate, ethyl lactate, isobutyl isobutyrate, 1, 4-butyrolactone, ethylene glycol monoacetate, ethylene glycol methyl ether acetate, ethylene glycol alkyl ether acetate, propylene glycol methyl ether acetate, ethyl 3-ethoxypropionate, ethoxyethyl acetate; cellosolve acetate, cellosolve esters of ethyl cellosolve acetate; toluene, aromatic hydrocarbons of xylene; ketones of acetone, butanone, cyclopentanone, cyclohexanone; amides of dimethylacetamide, N-methylpyrrolidone, dimethylformamide; chlorinated hydrocarbons of dichloromethane, dichloroethane, 1,1, 1-trichloroethane, chlorobenzene, o-dichlorobenzene; and mixtures of the foregoing;

5. The method according to claim 1, wherein the solution of the polymerization inhibitor or retarder in step S2 is composed of the following components in parts by weight:

polymerization inhibitor or retarder: 0.1% -50%;

other stabilizers: 0% -10%;

solvent: and (4) the balance.

6. The method according to claim 5, wherein the solution of the polymerization inhibitor or retarder in step S2 is composed of the following components in parts by weight:

polymerization inhibitor or retarder: 0.5% -10%;

other stabilizers: 1% -5%;

solvent: and (4) the balance.

7. The production method according to claim 6, wherein the polymerization inhibitor or retarder comprises an addition type polymerization inhibitor, a chain transfer type polymerization inhibitor and a charge transfer type polymerization inhibitor, the addition type polymerization inhibitor comprises quinones including benzoquinone, hydroquinone (hydroquinone), 2, 5-ditert-butyl hydroquinone, tert-butyl hydroquinone, naphthoquinone and hydroquinone monomethyl ether, nitro compounds including nitrobenzene, 1-methyl-3-nitrobenzene and polynitrobenzene, 2-sec-butyl-4, 6-dinitrophenol, sulfur compounds including 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxyl, and sulfur compounds including copper sulfide; the chain transfer polymerization inhibitor comprises 1, 1-diphenyl-2-trinitrophenylhydrazine, aromatic amine and phenols, wherein the aromatic amine comprises phenothiazine, N-methyl-N-nitrosoaniline and N-phenyl naphthylamine, and the phenols comprise resorcinol, 2, 6-di-tert-butyl-p-cresol and p-tert-butyl catechol; the charge transfer polymerization inhibitor comprises ferric chloride, copper chloride and a mixture of the ferric chloride and the copper chloride;

8. The manufacturing method according to claim 1, characterized in that: and the heat treatment in the step S3 comprises the treatment of a heating plate, a heating furnace, infrared heating equipment and microwave heating equipment, wherein the surface temperature of the substrate is 60-160 ℃, and the time is controlled within 10S-20 min.

9. The manufacturing method according to claim 1, characterized in that: the development in the step S4 is carried out for 20S-10min in TMAH or alkaline developer at the temperature of 20-50 ℃.