JP2010050231A - Chemical for dissolving and deforming and dissolving and deforming treatment method of organic film pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chemical for dissolving and deforming that includes at least one of an altered layer and a sedimentary layer and is capable of uniformly dissolving and deforming an organic film pattern having a barrier layer. <P>SOLUTION: The chemical for dissolving and deforming contains an alkali constituent A and an organic solvent B excluding amine. The constituent A is amine. The constituent B contains at least one of alcohols, ethers, esters, ketones, glycol ethers, nitriles, and amides. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a chemical solution for dissolution and deformation and a method for processing dissolution and deformation of an organic film pattern.

  Conventionally, after an organic film pattern is formed on a semiconductor wafer, an LCD (Liquid Crystal Display) substrate, or other substrate, the underlying film, that is, the substrate is subjected to pattern processing (underlayer processing) by etching using the organic film pattern as a mask. There is a technique for forming a wiring circuit or the like. Note that the organic film pattern is removed by a peeling process after the base film processing.

  For example, as shown in Patent Documents 1, 2, and 3, the organic film pattern is deformed after the base film processing, and the base film processing is performed again using the organic film pattern after the deformation as a mask. There is also a technique for removing the organic film pattern.

  More specifically, in the substrate processing method for processing the organic film pattern described in Patent Documents 1, 2, and 3, the main process is a dissolution deformation process in which the organic film pattern is deformed by dissolving the organic film pattern. Then, using the deformed organic film pattern as a mask, the base film is processed again, and then the organic film pattern is removed.

  The process for dissolving and deforming the organic film pattern is a process for reflowing the organic film pattern. For this reason, the dissolution deformation process is also called a dissolution deformation reflow process, a dissolution reflow process, or simply a reflow process.

  In addition, the dissolution deformation process is specifically performed by exposing the substrate to a gas atmosphere, and is also referred to as a gas atmosphere process.

  Furthermore, in order to stabilize the melt deformation process, heating is performed for the temperature adjustment process (mainly cooling) for adjusting the substrate temperature to an appropriate process temperature in advance and for baking the organic film pattern after the melt deformation process. It is common to add a process (this heat treatment may be realized by expanding the temperature adjustment range in the temperature adjustment processing apparatus).

Conventional dissolution deformation treatment (specifically, for example, gas atmosphere treatment) includes alcohols (R—OH), alkoxy alcohols, ethers (R—O—R, Ar—O—R, Ar—O—Ar). ), Vaporize solutions of organic solvents such as esters, ketones, glycols, alkylene glycols, glycol ethers (R represents an alkyl group or substituted alkyl group, Ar represents a phenyl group or an aromatic ring other than a phenyl group) This is performed by exposing the substrate to an atmosphere of a gas (specifically, vapor evaporated by heating or vapor generated by bubbling using an inert gas). In the dissolution deformation process, the organic film pattern dissolves when the organic chemical solution or the organic solvent penetrates into the organic film pattern, thereby causing liquefaction and fluidization (that is, dissolution deformation reflow).
JP 2002-334830 A JP 2005-159292 A JP 2005-159342 A

  By the way, in the dissolution deformation process of the organic film pattern, it is possible to cause a deformation of usually 5 to 20 μm, and a deformation of 100 μm or more is also possible. However, since the deformation amount is large, if the dissolution deformation (reflow) is not uniform, it is difficult to accurately deform the organic film pattern into the target shape. For this reason, when a certain degree of accuracy is required for the shape of the organic film pattern after reflow, it is necessary to perform reflow more uniformly.

  Further, when the organic film pattern is used for the reduction of the photolithography process, the source film / drain pattern mask (in this case, the resist pattern) for the source / drain formation mask in the channel portion, in particular, the source / drain region in the vicinity of the channel portion. A dissolution deformation process is used for the process of deforming the resist patterns separated into two into a desired shape and interconnecting them. However, in order to ensure the connection of the resist pattern, it is better to increase the amount of deformation by the melt deformation process, but the source / drain resist pattern such as the wiring portion other than the channel portion is also greatly melted and deformed. There was a problem. In order to avoid this problem, it is necessary to take measures such as forming the resist film thickness in two stages, and further removing the thinner one of the two-stage resist patterns before the melt deformation process. However, in this case as well, since the melt deformation process can only be controlled in one direction in which the area expands, the process time is controlled accurately so that the area does not expand more than necessary, thereby controlling the deformation with high precision. There was a need.

  Also, the surface layer of the organic film is altered by wet etching (for example, when the underlying layer of the organic film pattern is an Al film, wet etching using a mixed chemical solution of phosphoric acid, nitric acid, and acetic acid as an etchant). You can layer. Even if the organic film pattern in which the deteriorated layer is present is subjected to a dissolution deformation treatment with a conventional ordinary solvent, it reflows unevenly.

  In addition to the wet etching, the altered layer of the organic film pattern may be formed by the alteration of the surface layer of the organic film pattern due to at least one of the factors of time degradation, thermal oxidation, and thermal curing. is there. Furthermore, for example, a deposition layer may be formed on the surface of the organic film pattern by deposition by dry etching. In these cases as well, when the melt deformation treatment is performed with a conventional ordinary solvent, the reflow is unevenly performed.

  In short, when an altered layer or a deposited layer (hereinafter collectively referred to as an inhibition layer) is formed in the organic film pattern, the dissolution / deformation process is inhibited if the dissolution / deformation process is performed with a normal solvent. In addition, the reflow is not uniform.

  The present invention has been made to solve the above-described problems, and it is possible to accurately transform an organic film pattern into a target shape by dissolution and deformation treatment, and preferably, an altered layer and a deposited layer. It is an object of the present invention to provide a solution for dissolution and deformation and a method for dissolution and deformation which can perform uniform dissolution and deformation processing on an organic film pattern having an inhibition layer made of at least one of the above.

  In order to solve the above problems, a chemical solution for dissolution and deformation of the present invention is a chemical solution used for a dissolution and deformation process for dissolving and deforming an organic film pattern formed on a substrate, and comprises A) an alkali component and B) an amine. And an organic solvent to be excluded.

  Further, the chemical solution for dissolution and deformation of the present invention has an organic film pattern formed on a substrate, and a surface of the organic film pattern has an altered layer formed by altering the surface layer of the organic film pattern, and the organic film pattern A chemical solution for use in a dissolution / deformation process for dissolving / deforming the organic film pattern in the case where an inhibition layer comprising at least one of a deposition layer formed by depositing deposits on the surface is formed, It contains an alkali component and B) an organic solvent excluding amine.

  The organic film pattern dissolution / deformation processing method of the present invention causes the organic film pattern to be dissolved and deformed by bringing the chemical solution for dissolution / deformation of the present invention into liquid contact with the organic film pattern formed on the substrate. It is characterized by that.

  In addition, the organic film pattern dissolution and deformation treatment method of the present invention involves dissolving and deforming the organic film pattern by exposing the organic film pattern formed on the substrate to the vapor of the chemical solution for dissolution and deformation of the present invention. It is characterized by.

  According to the present invention, an organic film pattern can be accurately deformed into a target shape by a dissolution deformation process.

  In addition, a uniform dissolution deformation process can be performed on an organic film pattern having an inhibition layer composed of at least one of an altered layer and a deposited layer.

  Embodiments according to the present invention will be described below with reference to the drawings.

  Here, the dissolution deformation process described in the present embodiment is a process of dissolving (dissolving and deforming) an organic film pattern formed on the substrate by dissolving it.

  The dissolution deformation process is performed for the purpose of using the organic film pattern after the organic film pattern formed on the substrate is dissolved and deformed for a different use from the organic film pattern before the dissolution deformation.

  The process for dissolving and deforming the organic film pattern is a process for reflowing the organic film pattern. For this reason, the dissolution deformation process is also called a dissolution deformation reflow process, a dissolution reflow process, or simply a reflow process.

  Moreover, the chemical solution for dissolution deformation used for the dissolution deformation treatment is also referred to as a chemical solution for reflow.

[First Embodiment]
FIG. 1 is a series of process charts showing an example of a method for reducing the manufacturing process of a TFT substrate of a liquid crystal display device using the dissolution / deformation processing method performed using the dissolution / deformation chemical solution according to the present embodiment.

  In the present embodiment, an example in which the original organic film pattern 4 (see FIG. 1B) is formed by photolithography so as to have a plurality of stages (for example, two stages) of film thickness will be described.

  First, as shown in FIG. 1A, an organic film 3 is applied on a substrate 1 on which a semiconductor film 6 and a conductive film 2 are formed in this order.

  Next, by performing an exposure process in which the exposure amount is controlled in two or more stages, a development process, and a heating process as a pre-bake in this order, the film has a two-stage film thickness and is separated from each other. An initial organic film pattern 4 is formed on the substrate 1.

  As the exposure process here, for example, an exposure process in which continuous exposure is performed twice, a halftone mask exposure process using a pattern formed of a film having a transmittance of two or more steps as a mask, or a normal pattern and an exposure limit An exposure process using a gray-tone mask with the following fine pattern is performed.

  Specifically, for example, as shown in FIG. 1B, in each of a pair of organic film patterns 4 adjacent to each other, the portion close to the other organic film pattern 4 is thick, and the other The organic film patterns 4 that are separated from each other are formed so that the portion far from the organic film pattern 4 has a thin film thickness.

  Subsequently, the conductive film 2 is primarily patterned by performing an etching process (wet etching or dry etching) on the conductive film 2 on the substrate 1 using the original organic film pattern 4 as a mask. That is, a portion of the conductive film 2 that is not covered with the organic film pattern 4 is removed (FIG. 1C).

  Here, on the surface of the organic film pattern 4, an altered layer obtained by altering the surface layer portion of the organic film pattern 4 and a deposited layer obtained by depositing a deposit on the surface of the organic film pattern 4 are provided. The inhibition layer which consists of at least one of them is formed.

  If the inhibition layer includes an altered layer, is the altered layer, for example, whether the surface layer portion of the organic film pattern 4 has been altered due to at least one of the following factors: time degradation, thermal oxidation, and thermosetting Alternatively, the surface layer portion of the organic film pattern 4 may be altered by wet etching treatment, or the surface layer portion of the organic film pattern 4 may be altered by dry etching or ashing treatment. Moreover, when a deposition layer is included in the inhibition layer, the deposition layer is, for example, a layer deposited on the surface of the organic film pattern 4 by deposition by dry etching.

  Subsequently, re-development processing is performed, and further, after the re-development processing, the original organic film pattern 4 is processed into a new pattern-shaped organic film pattern 5 by performing heat treatment that is pre-baking again. That is, by reworking the organic film pattern 4 so that the planar existence range on the conductive film 2 is reduced, the thin portion of the organic film pattern 4 is removed, and the film thickness is only one level. An organic film pattern 5 is formed (FIG. 1D).

  Next, the dissolution deformation process according to the present embodiment is performed on the organic film pattern 5 using the dissolution deformation chemical solution (described later) according to the present embodiment. Thereby, as shown in FIG. 1E, adjacent organic film patterns 5 are integrated with each other to be processed into one new organic film pattern 7. As a result, as shown in FIG. 1E, a portion of the semiconductor film 6 located between a pair of adjacent conductive films 2 is covered with the organic film pattern 7.

  Subsequently, the semiconductor film 6 is etched (dry etched) using the new organic film pattern 7 and the conductive film 2 therebelow as a mask (FIG. 1E).

  Thereafter, the organic film pattern 7 is peeled and removed (FIG. 1F).

  Next, the chemical solution for dissolution deformation according to this embodiment will be described.

  Conventionally, when the inhibition layer as described above is formed in an organic film pattern, even if the organic film pattern is subjected to a reflow treatment with a normal solvent, the reflow becomes non-uniform. Therefore, there has been a demand for a solution solution for dissolution deformation and a dissolution deformation treatment method capable of uniform dissolution deformation even in the presence of an inhibition layer.

  As a result of the examination, when the dissolution / deformation treatment is performed using a chemical solution for dissolution / deformation containing A) an alkali component and B) an organic solvent excluding the amine, even an organic film pattern having an inhibition layer is uniformly dissolved. It turns out that it transforms. Moreover, the chemical solution for dissolution deformation may further contain C) water.

  First, A) the alkali component will be described.

  It is considered that the alkaline component is adsorbed on the surface of the organic film pattern and the inhibitory layer is modified to enable uniform dissolution deformation reflow.

  Specific examples of the alkali component include amines, ammonia, alkylammonium hydroxide, and the like, and amines are preferred because of their efficacy and ease of handling. Of the amines, monoethanolamine, isopropanolamine, N-methylethanolamine, N, N-dimethylethanolamine, and morpholine are particularly suitable. One alkali component may be used, or two or more alkali components may be mixed.

  The content of component A is preferably 0.2% by weight to 30% by weight. If it is less than 0.2% by weight, the ability to make the reflow uniform is not sufficiently exhibited, and if it exceeds 30% by weight, the reflow rate (the rate of dissolution and deformation) may be significantly reduced.

  Next, B) an organic solvent excluding amine will be described.

  B) The organic solvent excluding the amine is the main component to be reflowed.

  The organic solvent excluding the amine is not limited as long as it has a vapor pressure in the process conditions (temperature, atmospheric pressure) of the dissolution deformation treatment. Specific examples include alcohols, ethers, esters, ketones, glycol ethers, nitriles, amides, and the like. Of these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl isobutyl ketone, acetonitrile, and N, N-dimethylacetamide are particularly suitable. One organic solvent may be used, or two or more organic solvents may be mixed.

  The content of component B is preferably 40% by weight to 99.8% by weight. If the amount is less than 40% by weight, the reflow rate is remarkably reduced, and if it exceeds 99.8% by weight, the reflow may be uneven. When the solution for dissolution and deformation does not contain the C component, the content of the B component is desirably 70% by weight or more.

  Next, C) water will be described.

  The water component C) can be used to adjust the reflow rate or to reduce the content of organic components.

  The water content is preferably 60% by weight or less, and more preferably 50% by weight or less. If it exceeds 60% by weight, the reflow rate may be significantly reduced. The total of the content of the C component and the content of the B component is preferably 70% by weight or more.

  In addition, the case where the sum total of A component, B component, and C component will be 100 weight%, and the chemical solution for dissolution deformation containing an additive other than A component, B component, and C component may be used. In the latter case, for example, a surfactant can be used as the additive.

  Next, the dissolution deformation process will be described.

  The dissolution deformation treatment can be suitably performed by bringing vapor generated by bubbling the dissolution deformation chemical liquid with an inert gas into contact with the organic film pattern. The dissolution deformation process in this case is referred to as a gas atmosphere process.

  However, the dissolution deformation treatment can also be performed by bringing the dissolution deformation chemical liquid into contact with the organic film pattern in a liquid state.

  The dissolution deformation process may be completed only once, but the second dissolution deformation process may be performed as necessary. However, as the chemical solution for dissolution deformation used for the second dissolution deformation treatment, it is preferable to use a chemical solution that is different from the above-described chemical solution for dissolution deformation in that it does not contain an alkali component.

  This is because it is effective to divide into two steps in this way because the reflow rate may be remarkably lowered when an alkali component is contained in the solution for dissolution and deformation used in the second dissolution and deformation treatment.

  Next, an example will be described in which the results of the dissolution / deformation process according to the composition of the dissolution / deformation chemical solution are evaluated.

  FIG. 2 shows the composition of the chemical solution for dissolution and deformation used in the first dissolution and deformation treatment for each of Examples 1 to 11 and Comparative Examples 1 to 5 (column of “first reflow” in FIG. 2), 2 The presence / absence of the second dissolution / deformation process (in the column “Presence / absence of second time” in FIG. 2) and the composition of the chemical solution for dissolution / deformation used for the second dissolution / deformation process (“Reflow” in FIG. 2) It is a figure which shows the result (column of "result" of FIG. 2) and the result (column of "result" of FIG. 2).

  As shown in FIG. 2, in Examples 1 to 10 and Comparative Examples 1 to 4, the dissolution deformation process was performed only once. Moreover, in Example 11 and Comparative Example 5, the dissolution deformation process was performed twice.

  Specifically, in Example 1, a chemical solution for dissolution deformation comprising 10% by weight of monoethanolamine as the component A and 90% by weight of propylene glycol monomethyl ether as the component B was used.

  In Example 2, a solution for dissolution deformation comprising 10% by weight monoethanolamine as component A, 30% by weight propylene glycol monomethyl ether as component B, and 60% by weight propylene glycol monomethyl ether acetate. Using.

  In Example 3, a chemical solution for deformation and deformation comprising 10% by weight of monoethanolamine as the A component and 90% by weight of methyl isobutyl ketone as the B component was used.

  In Example 4, a chemical solution for dissolution and deformation comprising 5% by weight of monoethanolamine as the A component and 95% by weight of N, N-dimethylacetamide as the B component was used.

  In Example 5, a chemical solution for dissolution deformation comprising 5% by weight of N-methylethanolamine as the A component and 95% by weight of N, N-dimethylacetamide as the B component was used.

  In Example 6, a chemical solution for dissolution and deformation comprising 10% by weight of isopropanolamine as the A component and 90% by weight of propylene glycol monomethyl ether as the B component was used.

  In Example 7, a chemical solution for dissolution deformation comprising 10% by weight of N, N-dimethylethanolamine as the A component and 90% by weight of propylene glycol monomethyl ether as the B component was used.

  In Example 8, a chemical solution for deformation and deformation comprising 10% by weight of morpholine as the A component and 90% by weight of propylene glycol monomethyl ether as the B component was used.

  In Example 9, a solution for dissolution and deformation comprising 5% by weight of monoethanolamine as the component A, 20% by weight of acetonitrile as the component B, and 75% by weight of propylene glycol monomethyl ether acetate was used.

  In Example 10, 5 wt% monoethanolamine as component A, 20 wt% acetonitrile as component B, 55 wt% propylene glycol monomethyl ether acetate, and 20 wt% pure water as component C A solution for dissolution deformation consisting of

  In the first dissolution deformation treatment of Example 11, a dissolution deformation chemical solution comprising 10% by weight of monoethanolamine as the A component and 90% by weight of diethylene glycol monobutyl ether as the B component was used. In the second dissolution deformation treatment of Example 11, a chemical solution for dissolution deformation composed of 100% by weight of propylene glycol monomethyl ether was used.

  In Comparative Example 1, a chemical solution for dissolution and deformation comprising 100% by weight of monoethanolamine as the component A was used.

  In Comparative Example 2, a chemical solution for dissolution and deformation composed of 100% by weight of propylene glycol monomethyl ether as component B was used.

  In Comparative Example 3, a chemical solution for dissolution and deformation comprising 100% by weight of propylene glycol monomethyl ether acetate as component B was used.

  In Comparative Example 4, a chemical solution for dissolution and deformation comprising 100% by weight of isopropanolamine as the B component was used.

  In the first dissolution deformation treatment of Comparative Example 5, a chemical solution for dissolution deformation composed of 100% by weight of diethylene glycol monobutyl ether as the B component was used. In the second dissolution deformation treatment of Comparative Example 5, a chemical solution for dissolution deformation composed of 100% by weight of propylene glycol monomethyl ether was used.

  FIG. 3 is a view showing a cross-sectional structure of the evaluation substrate 10 used in each of Examples 1 to 11 and Comparative Examples 1 to 5.

  The evaluation board | substrate shown in FIG. 3 was created in the procedure demonstrated below.

  First, the Al film 12 is formed on the glass substrate 11.

  Next, a positive photoresist is applied on the Al film 12, and the photoresist is exposed and developed to form an organic film pattern 13.

  Next, using the organic film pattern 13 as a mask, the Al film 12 was etched with an etching solution using a mixed chemical solution of phosphoric acid / nitric acid / acetic acid, thereby producing the evaluation substrate 10 of FIG.

  In addition, since the evaluation board | substrate 10 was produced in this way, when the Al film | membrane 12 is etched, the inhibition layer (specifically, altered layer) is formed in the surface layer part of the organic film pattern 13. FIG.

  All evaluations were performed at room temperature.

  A specific evaluation procedure will be described below.

  First, a chemical solution for dissolution and deformation was placed in a petri dish. At this time, the amount of the chemical solution was adjusted so that the distance from the surface of the chemical solution for dissolution deformation to the mouth of the petri dish was 1 cm.

Subsequently, the petri dish was completely covered with the evaluation substrate 10 so that the organic film pattern was on the bottom (so that the vapor of the chemical solution for dissolution and deformation was in contact with the organic film pattern). After 30 seconds, the evaluation substrate 10 was removed from the petri dish, and N ₂ gas was sprayed with an N ₂ gun to dry the evaluation substrate.

  Thus, the first melting / deforming process is completed.

  When the dissolution / deformation treatment was performed twice, the second dissolution / deformation treatment was performed in the same procedure as the first time using another petri dish and a second dissolution / deformation chemical solution.

  And the evaluation board | substrate 10 after a process was observed with the optical microscope, and the reflow condition of the organic film pattern was confirmed.

  In the result column of FIG. 2, “◯” indicates that the organic film pattern is reflowed uniformly, “×” indicates that the organic film pattern is reflowed unevenly, and “no change” indicates that the organic film pattern is reflowed. Indicates that no change occurred.

  That is, as shown in FIG. 2, the organic film pattern was reflowed uniformly in all the examples (Examples 1 to 11).

  On the other hand, when a chemical solution for dissolution / deformation containing only amine (Comparative Example 1) or a chemical solution for dissolution / deformation consisting only of an organic solvent excluding amine (Comparative Examples 2 to 5) is used, the organic film pattern does not reflow. (Comparative Examples 1 and 3) or even if reflowed, it was non-uniform (Comparative Examples 2, 4, and 5).

  The reason why non-uniform reflow occurs other than the conventional chemical solution for dissolution and deformation and the chemical solution for dissolution and deformation of the present embodiment is that the surface of the organic film pattern is altered by the etching solution, and the chemical solution for dissolution and deformation enters the organic film pattern inside. In some cases, the penetration may be inhibited or the penetration may be promoted. Further, depending on the degree of alteration (WE: wet etching treatment conditions or organic film formation conditions), the thickness of the altered portion is partially This is because when the thickness is too thin, the partial penetration of the solution for dissolution and deformation and the uniformity over the entire substrate may be poor.

  Here, the case where the organic film pattern normally reflows in the dissolution deformation process and the case where the organic film pattern reflows abnormally (such as non-uniformity) will be described with reference to FIG.

  FIG. 4 is a diagram illustrating how the planar shape and the cross-sectional shape of the organic film pattern change due to the dissolution deformation process.

  FIG. 4A shows a planar shape (left diagram) and a cross-sectional shape (right diagram) of the organic film pattern 20 before the dissolution deformation process.

  FIG. 4B shows a planar shape (left diagram) and a cross-sectional shape (right diagram) when the organic film pattern 20 is uniformly reflowed by the dissolution deformation process, that is, when the dissolution deformation process is normal. In this case, the organic film pattern 20 spreads uniformly, the channel portions are combined, and other portions are spread uniformly. When the dissolution / deformation treatment is performed using the dissolution / deformation chemical solution according to the present embodiment, the dissolution / deformation chemical solution penetrates uniformly into the organic film pattern 20, and the organic film pattern 20 is almost uniformly dissolved. Dissolution at a rate occurs. For this reason, as shown in FIG. 4B, the entire organic film pattern 20 reflows integrally, so that the organic film pattern 20 can be accurately deformed to a target shape.

  FIG. 4C shows an abnormality that occurs when the reflow rate is different between the surface layer portion and the inside of the organic film pattern 20. In this case, the reflow is divided into two, ie, an organic film pattern 21 that is thin and wide and an organic film pattern 22 that is thick and small.

  FIG. 4D shows an abnormality that occurs when a deteriorated layer partially remains in the surface layer portion of the organic film pattern 20. In this case, the direction in which the organic film pattern 20 reflows and spreads is non-uniform and scattered. For this reason, the organic film pattern coupling | bonding of the target channel part does not occur, but parts other than a channel part reflow and spread.

  FIG. 5 is a diagram illustrating a state in which the cross-sectional shape of the organic film pattern is changed by performing the dissolution deformation process when a deteriorated layer is formed in the developed organic film pattern.

  FIG. 5A shows a cross-sectional shape of the organic film pattern 30 after development.

  FIG. 5B shows a state in which the altered layer 32 is formed in the surface layer portion of the organic film pattern 30 as a result of etching the base film 31 by wet etching after development.

  FIG. 5C and FIG. 5D show a dissolution deformation process using a conventional chemical solution. In this case, the reflow rate is different between the surface of the organic film pattern 30 and the inside, resulting in non-uniform reflow. That is, for example, the organic film pattern 30 has a fast reflow rate only on a part of its surface (the part at the bottom), and does not become an integral reflow of the entire organic film pattern 30. In other words, a part of the surface of the organic film pattern 30 reflows with low viscosity, while the inside of the organic film pattern 30 has high viscosity and does not reflow so much. For this reason, the inside of the organic film pattern 30 tends to remain difficult to reflow, while the peripheral portion of the organic film pattern 30 spreads thinly (FIG. 5D). Further, the spread of the organic film pattern 30 tends to occur.

  On the other hand, FIG.5 (E) and FIG.5 (F) show a dissolution deformation | transformation process using the chemical | medical solution for dissolution deformation | transformation which concerns on this embodiment. In this case, the inside of the organic film pattern 30 is dissolved at a substantially uniform reflow rate, and integral reflow of the entire organic film pattern 30 occurs. In other words, the entire organic film pattern 30 is reflowed into a liquid state with a uniform viscosity. For this reason, the joint portion of the pair of organic film patterns 30 rises due to the surface tension and increases in thickness as compared with the case of FIG. Therefore, the pattern in which the pair of organic film patterns 30 are combined can be made as an organic film pattern formed integrally from the beginning. Further, the spread of the organic film pattern 30 can be suppressed as much as possible. In addition, the spread of the organic film pattern 30 hardly occurs. Therefore, the organic film pattern 30 can be accurately deformed to the target shape. In addition, uniform dissolution deformation processing can be performed on the organic film pattern 30 having the inhibition layer (for example, the altered layer).

  According to the first embodiment as described above, the organic film pattern can be accurately deformed into a target shape by performing the dissolution deformation process using the dissolution deformation chemical solution according to the present embodiment. In addition, a uniform dissolution deformation process can be performed on an organic film pattern having an inhibition layer composed of at least one of an altered layer and a deposited layer.

  In addition, also when performing a dissolution deformation process (for example, the process performed after FIG. 1D) using the chemical solution for dissolution deformation according to the present embodiment, the inhibition layer makes the dissolution deformation process difficult. There is. In addition, the inhibition layer may make the above-described redevelopment processing (for example, processing performed after FIG. 1C) difficult.

  For this reason, subsequent to FIG. 1C, the inhibition layer is made brittle (weakened) to facilitate re-development processing and dissolution deformation processing, or the inhibition layer is organically treated. A removal process for facilitating the redevelopment process and the dissolution deformation process by removing the film pattern 4 may be performed as necessary.

  This removal process is described in detail in, for example, Patent Documents 2 and 3, JP-A-2008-72059, JP-A-2007-317983, JP-A-2007-256666, etc. Omitted.

  Further, since the weakening process is the same process as the removal process, detailed description thereof is omitted. If the inhibition layer is strong, even if a removal process (originally aimed at removing the inhibition layer) is performed, the inhibition layer may not be completely removed, and the inhibition layer may be weakened. . In other words, in this case, the process similar to the removal process is substantially a weakening process, and thus is referred to as such.

[Second Embodiment]
In the second embodiment, an example of a method for reducing the manufacturing process of the TFT substrate of the liquid crystal display device by using the dissolution / deformation processing method performed using the same solution for dissolution / deformation as in the first embodiment ( An example different from the first embodiment (FIG. 1) will be described.

  6A to 6G are diagrams showing a series of steps for manufacturing a TFT substrate of a liquid crystal display device in the case of the second embodiment, and a plan view and a cross-sectional view of the TFT element, respectively.

  In this embodiment, an example in which the number of processes is reduced by using halftone mask exposure will be described.

  Here, halftone mask exposure will be described. First, a photosensitive organic film (hereinafter, a resist film is shown as an example) pattern is formed so as to have a plurality of stages of film thickness differences. For example, the resist film is formed in a plurality of stages by exposing the resist film twice continuously or by using an exposure mask in which the transmission amount is changed stepwise at the time of one exposure.

  When the thin film portions of the multi-stage (for example, two stages) resist film are removed by ashing or the like, the pattern of the resist film changes before and after the removal.

  For this reason, if the resist film is used as a resist mask before and after the removal of the thin film portion, the same effect as in the case where the resist film is formed twice by carrying out the lithography process twice is obtained in one lithography process. Obtainable.

  That is, the lower layer film is etched using the resist film before removal of the thin film portion as a resist mask, and then the lower layer film is etched using the resist film after removal of the thin film portion as a resist mask. Different types of patterns can be formed.

  It is well known that such a technique is used as a new process for reducing the cost, and generally in a process of 5PR process → 4PR process as a reduction of the photograph process for forming the TFT element.

  Further, a light shielding portion and a semi-translucent portion are formed in a reticle mask pattern used in a photolithography process, and the light shielding portion and the semi-transparent portion are transferred to a resist film to form the first resist mask. Is done.

  As a method of forming the semi-translucent portion, there are the following methods (1) and (2).

  (1) A method of forming a pattern in which the same material as the material of the light shielding portion (mainly chromium film) is processed to a dimension below the resolution limit.

  (2) A method of forming a material (for example, a film of chromium oxide film, tungsten silicide, etc.) with a material (mainly chromium film) of the light shielding portion and a different material having a higher transmittance than the material of the light shielding portion.

  Hereinafter, the manufacturing method of FIG. 6 will be described.

  First, as shown in FIG. 6A, a gate wiring 2001 is formed over a glass substrate (not shown).

Next, an interlayer insulating film (for example, a single-layer film or a two-layer film of a silicon oxide film (SiO ₂ ) or a silicon nitride film (SINx)) 2002 is formed so as to cover the gate wiring 2001.

  Next, a semiconductor film 2003 including an amorphous silicon (a-Si) layer and an ohmic contact (n + a-Si) layer and a drain wiring metal film 2004 are stacked on the interlayer insulating film 2002. Here, the ohmic contact layer is composed of an n-type amorphous silicon (n + a-Si) layer doped with phosphorus impurities.

  Next, an organic film (for example, a resist film) is applied on the drain wiring metal film 2004.

  Next, an organic film (hereinafter referred to as “resist”) pattern is formed by exposure processing and development processing using an exposure mask (halftone mask). Here, a resist pattern 2005 having a two-stage film thickness is formed.

  Next, as shown in FIG. 6B, the base film, that is, the drain wiring metal film 2004 is etched using the resist pattern 2005 as a mask. By this etching, the drain wiring metal film 2004 becomes a source / drain electrode and a source / drain wiring.

  Next, as shown in FIG. 6C, a dissolution deformation process is performed on the resist pattern 2005.

  This dissolution deformation process is, for example, a gas atmosphere process performed by exposing the organic film pattern to the vapor of the chemical solution for dissolution deformation described in the first embodiment.

  6C, the source electrode resist mask and the drain electrode resist mask are reflowed in the horizontal direction, and the source resist mask and the drain electrode resist mask are connected to each other. A connected resist mask 2006 is obtained.

  However, if necessary, the first removal process (or the first weakening process) may be performed before the dissolution deformation process.

  This first removal process (or first weakening process) is the same as the removal process (weakening process) described in the first embodiment, and at least an inhibition layer on or around the resist pattern. This is done for the purpose of removal (or weakening).

  Next, as shown in FIG. 6D, the connected resist mask is obtained only by the second removal process or by a combination of the first removal process (or the first weakening process) and the second removal process. At least a part of 2006 is removed. The second removal process can be performed, for example, by a development process using a development functional solution.

  Here, the thick part of the resist pattern having the two-stage film thickness is removed. In this case, it is possible to remove a part of the resist mask whose area is enlarged mainly by the dissolution deformation process, that is, an unnecessary chemical solution reflow part, and the final organic film pattern is accurately formed into a desired pattern shape. It is possible to form well.

  Next, as shown in FIG. 6E, an amorphous silicon (a-Si) layer and an ohmic contact (n + a-Si) layer are formed using the connection resist mask 2006, the source / drain electrodes, and the source / drain wirings as a mask. The semiconductor film 2003 made of is removed by etching to form a semiconductor island 2007.

  Next, as shown in FIG. 6F, the connection resist mask 2006 is peeled off from the semiconductor island 2007 and removed.

  Next, as shown in FIG. 6G, CH (channel) etching is performed using the exposed source / drain electrodes and source / drain wirings as a mask. By this CH (channel) etching, at least the upper ohmic contact (n + a-Si) layer of the semiconductor film 2003 composed of the amorphous silicon (a-Si) layer between the source and the drain and the ohmic contact (n + a-Si) layer is removed. Then, at least a part of the amorphous silicon (a-Si) layer is left.

  Although the subsequent steps are omitted, a passivation film (insulating film: usually a plasma silicon nitride film) is formed, contact holes are formed on the source electrode and the drain electrode, and the source is formed at the bottom of these contact holes. A pixel electrode connected to the electrode and a terminal electrode connected to the drain electrode are formed.

  In this way, a TFT substrate is formed, and then, a counter substrate facing the TFT substrate is arranged on the semiconductor island 2007 side of the TFT substrate. Further, a liquid crystal composition is filled between the TFT substrate and the counter substrate to complete a liquid crystal display device.

  Note that the CH (channel) etching can also be performed after the etching of the drain wiring metal film 2004 using the resist pattern 2005 as a mask (FIG. 6B). In this case, after the connection resist mask 2006 is removed from the semiconductor island 2007 (FIG. 6F), at least a part of the amorphous silicon (a-Si) of the channel portion that has been contaminated or has been altered so far. It is preferred that the layer be slightly etched away or surface treated. However, also in this case, most of the amorphous silicon (a-Si) layer needs to remain.

  According to the second embodiment as described above, the same effects as those of the first embodiment can be obtained.

[Third Embodiment]
In the third embodiment, a method for reducing the manufacturing process of a TFT substrate of a liquid crystal display device by using a dissolution / deformation treatment method performed using the same chemical solution for dissolution / deformation as in the first and second embodiments. An example (an example different from the above-described first and second embodiments (FIGS. 1 and 6)) will be described.

  FIGS. 7A to 7G are views showing a series of steps for manufacturing a TFT substrate of a liquid crystal display device in the case of the third embodiment, and show a plan view and a sectional view of the TFT element, respectively.

  Unlike the second embodiment, this embodiment uses a normal standard mask without using halftone mask exposure.

  First, as shown in FIG. 7A, a gate wiring 3001 is formed over a glass substrate (not shown).

Next, an interlayer insulating film (for example, a single-layer or two-layer film of a silicon oxide film (SiO ₂ ) or a silicon nitride film (SINx)) 3002 is formed so as to cover the gate wiring 3001.

  Next, a semiconductor film 3003 including an amorphous silicon (a-Si) layer and an ohmic contact (n + a-Si) layer and a drain wiring metal film 3004 are stacked on the interlayer insulating film 3002. Here, the ohmic contact layer is composed of an n-type amorphous silicon (n + a-Si) layer doped with phosphorus impurities.

  Next, an organic film (for example, a resist film) is applied on the drain wiring metal film 3004.

  Next, an organic film (hereinafter referred to as “resist”) pattern 3005 is formed by exposure processing and development processing using an exposure mask (standard mask).

  Next, as shown in FIG. 7B, the base film, that is, the drain wiring metal film 3004 is etched using the resist pattern 3005 as a mask. By this etching, the drain wiring metal film 3004 becomes a source / drain electrode and a source / drain wiring.

  Next, as shown in FIG. 7C, the dissolution deformation process similar to that in the first and second embodiments is performed on the resist pattern 3005.

  7C, the source electrode resist mask and the drain electrode resist mask are reflowed in the horizontal direction, and the source resist mask and the drain electrode resist mask are connected to each other. A connected resist mask 3006 is obtained.

  However, if necessary, the first removal process (or the first weakening process) may be performed before the dissolution deformation process. This first removal process (or first weakening process) is the same as in the second embodiment.

  Next, as shown in FIG. 7D, the connected resist mask is obtained only by the second removal process or by a combination of the first removal process (or the first weakening process) and the second removal process. At least a portion of 3006 is removed. This second removal process is the same as in the second embodiment.

  Here, a part of the connected resist mask 3006 whose area has been expanded by the dissolution deformation process, that is, an unnecessary dissolution deformation portion can be removed, and the final organic film pattern can be accurately formed into a target shape. It becomes possible.

  Next, as shown in FIG. 7E, an amorphous silicon (a-Si) layer and an ohmic contact (n + a-Si) layer are formed using the connection resist mask 3006, the source / drain electrodes, and the source / drain wirings as a mask. The semiconductor film 3003 made of is removed by etching to form a semiconductor island 3007. In FIG. 7E, this is indicated as a-Si etching.

  Next, as shown in FIG. 7F, the connection resist mask 3006 is peeled off from the semiconductor island 3007 and removed.

  Next, as shown in FIG. 7G, CH (channel) etching is performed using the exposed source / drain electrodes and source / drain wirings as a mask. By this CH (channel) etching, at least the upper ohmic contact (n + a-Si) layer of the semiconductor film 3003 composed of the amorphous silicon (a-Si) layer between the source and drain and the ohmic contact (n + a-Si) layer is removed. And at least a part of the amorphous silicon (a-Si) layer remains.

  Although the subsequent steps are omitted, a passivation film (insulating film: usually a plasma silicon nitride film) is formed, contact holes are formed on the source electrode and the drain electrode, and the source is formed at the bottom of these contact holes. A pixel electrode connected to the electrode and a terminal electrode connected to the drain electrode are formed.

  In this way, the TFT substrate is formed, and subsequently, a counter substrate facing the TFT substrate is disposed on the semiconductor island 3007 side of the TFT substrate. Further, a liquid crystal composition is filled between the TFT substrate and the counter substrate to complete a liquid crystal display device.

  Note that the CH (channel) etching can also be performed after the etching of the drain wiring metal film 3004 using the resist pattern 3005 as a mask (FIG. 7B). In this case, after the connection resist mask 3006 is removed from the semiconductor island 3007 (FIG. 7F), at least a part of the amorphous silicon (a-Si) of the channel portion that has been contaminated or has been altered so far. It is preferred that the layer be slightly etched away or surface treated. However, also in this case, most of the amorphous silicon (a-Si) layer needs to remain.

  According to the third embodiment as described above, the same effects as those of the first and second embodiments can be obtained.

  In the second and third embodiments, the gate electrode, the source electrode, the drain electrode, and the drain wiring metal film of the thin film transistor are made of a single layer structure of aluminum or aluminum alloy, a single layer structure of chromium or chromium alloy, aluminum or Two-layer structure of aluminum alloy and chromium or chromium alloy, two-layer structure of aluminum or aluminum alloy and titanium or titanium alloy, two-layer structure of aluminum or aluminum alloy and titanium nitride or titanium nitride alloy, aluminum or aluminum alloy Two-layer structure of molybdenum and molybdenum or molybdenum alloy, Two-layer structure of chromium or chromium alloy and molybdenum or molybdenum alloy, Three layers of chromium or chromium alloy, aluminum or aluminum alloy, and chromium or chromium alloy Three-layer structure of molybdenum or molybdenum alloy and aluminum or aluminum alloy and molybdenum or molybdenum alloy, three-layer structure of aluminum or aluminum alloy and molybdenum or molybdenum alloy and chromium or chromium alloy, aluminum or aluminum alloy and molybdenum or molybdenum What is necessary is just to be comprised from either the three-layer structure of an alloy and titanium or a titanium alloy, or the three-layer structure of aluminum or an aluminum alloy and titanium nitride or a titanium nitride alloy, and titanium or a titanium alloy.

  In the second and third embodiments described above, the glass substrate is used. However, the present invention is not limited to this, and an insulating substrate made of another material can also be used.

  In the above embodiment, the formation method up to the staggered TFT pattern has been described. However, the pattern formation method according to the present invention is not limited to this, and among the above-described TFT pattern formation methods, The present invention can also be applied to the formation of a color filter layer or a TFT pattern with a color filter in which a planarizing film and a color filter layer are formed below the electrode.

  Further, in the above embodiment, the present invention has been described by taking the vertical electric field drive type liquid crystal display device as an example. However, the present invention is not limited to this, and the present invention is not limited to the horizontal electric field drive type liquid crystal display device (IPS (In-Plane). (Switching) LCD).

  The pattern forming method described in the second and third embodiments can be used as a method for manufacturing a TFT substrate. An example of the TFT substrate is a TFT substrate for a liquid crystal display device.

  In addition, after the TFT substrate is fabricated, an insulating film, a color (RGB: red, green, blue) filter layer and a black matrix layer, a color filter formed with a transparent electrode or a single color filter is formed, and then a pixel electrode such as ITO, orientation A liquid crystal display device can be manufactured by forming a film and other components, sandwiching and sealing a liquid crystal between a TFT substrate and a counter substrate, and further attaching a polarizing filter to both substrates.

  As a method for partially controlling the thickness of the resist mask, for example, there is the following method.

(1) The mask pattern of the reticle used in the exposure process includes a light-shielding portion and a semi-light-shielding portion controlled to at least two levels of transmitted light amount. Method of transferring and forming resist mask (2) Method of forming resist mask by using two or more reticle masks in the exposure step and changing the exposure amount in at least two stages Here, mainly, Using a halftone mask, the resist mask film thickness was partially controlled to form a resist pattern having a two-stage film thickness. This resist pattern became a reticle having a light-shielding portion and a semi-translucent portion. Yes.

  Hereinafter, a specific example of this resist pattern forming method will be described.

(Example 1)
On the reticle substrate, for example, a light shielding portion and a semi-transparent portion are formed of chromium metal.

  This semi-translucent portion is composed of a chromium metal pattern having an exposure resolution limit or less. For example, rectangular patterns having a pattern width dimension equal to or smaller than the exposure wavelength are arranged at a predetermined pitch. Alternatively, such a rectangular pattern is formed in a lattice shape.

  In the region where the chromium metal pattern below the exposure resolution limit is formed, the transmission amount of the exposure irradiation light is set to 20 to 80%. In this way, a semi-translucent part is formed.

(Example 2)
On the reticle substrate, for example, a light shielding portion is formed in a predetermined pattern with chromium metal. The chromium metal in the region that becomes the semi-translucent portion is etched to form a thin film portion.

  In the region where the chromium metal thin film portion is formed, about half of the exposure light is transmitted. In this way, a semi-translucent portion is formed.

(Example 3)
On the reticle substrate, for example, a light shielding portion is formed in a predetermined pattern with chromium metal. The semi-translucent part is formed as a halftone part.

  Here, the halftone portion is formed of, for example, tungsten silicide, molybdenum silicide, or the like. In this way, a semi-translucent part is formed.

It is a figure which shows a series of processes which manufacture the TFT substrate of a liquid crystal display device using the melt | dissolution deformation processing method which concerns on embodiment. It is a figure which shows the effect of an Example and its comparative example for every composition of the chemical solution for dissolution deformation. It is a figure which shows the cross-section of the evaluation board | substrate used for the Example and its comparative example. It is a figure which shows a mode that the planar shape and cross-sectional shape of an organic film pattern change by implementation of a melt | dissolution deformation process. It is a figure which shows a mode that the shape of an organic film pattern changes by implementation of the melt | dissolution deformation process with respect to the organic film pattern in which the deteriorated layer was formed. It is a figure which shows a series of processes which manufacture the TFT substrate of a liquid crystal display device in 2nd Embodiment. It is a figure which shows a series of processes which manufacture the TFT substrate of a liquid crystal display device in 3rd Embodiment.

Explanation of symbols

5, 13, 20, 30, 2005, 3005 organic film pattern

Claims (17)

A chemical solution used for dissolution and deformation processing for dissolving and deforming an organic film pattern formed on a substrate,
A) an alkali component;
B) an organic solvent excluding amine,
A chemical solution for dissolution and deformation. An organic film pattern is formed on a substrate, a modified layer obtained by altering a surface layer of the organic film pattern on the surface of the organic film pattern, and a deposit formed by depositing a deposit on the surface of the organic film pattern When the inhibition layer consisting of at least one of the layers is formed, it is a chemical solution used for a dissolution deformation process for dissolving and deforming the organic film pattern,
A) an alkali component;
B) an organic solvent excluding amine,
A chemical solution for dissolution and deformation. The chemical solution for dissolution deformation according to claim 1 or 2, wherein the component A is an amine. The component A is at least one selected from the group consisting of monoethanolamine, isopropanolamine, N-methylethanolamine, N, N-dimethylethanolamine, and morpholine. The chemical solution for dissolution deformation according to any one of the above. The said B component is an organic solvent containing at least any one of the organic solvents shown in the following (1)-(7), It is any one of Claims 1 thru | or 4 characterized by the above-mentioned. Chemical solution for dissolution and deformation.
(1) Alcohols (2) Ethers (3) Esters (4) Ketones (5) Glycol ethers (6) Nitriles (7) Amides The component B contains at least one of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl isobutyl ketone, acetonitrile, and N, N-dimethylacetamide. The chemical solution for dissolution deformation according to one item. Furthermore, C) water is contained, The chemical | medical solution for dissolution deformation | transformation as described in any one of Claim 1 thru | or 6 characterized by the above-mentioned. 7. The dissolution according to claim 1, wherein the content of the A component is 0.2 to 30% by weight and the content of the B component is 70 to 99.8% by weight. Deformation chemical. The content of the component A is 0.2 to 30% by weight, the content of the component B is 40 to 99.8% by weight, the content of the component C is 59.8% by weight or less, 8. The solution for dissolution deformation according to claim 7, wherein the total content of the C component is 70% by weight or more.   The said chemical solution for dissolution deformation is used for the dissolution deformation process which melts and deforms the said organic film pattern by making the said chemical solution of the chemical liquid for dissolution deformation contact with the said organic film pattern as a liquid. The chemical solution for dissolution deformation according to any one of 9.   10. The dissolution deformation chemical solution is used for a dissolution deformation process in which the organic film pattern is dissolved and deformed by exposing the organic film pattern to vapor of the dissolution deformation chemical solution. The chemical solution for dissolution deformation according to claim 1. The organic film pattern formed on the substrate is dissolved and deformed by bringing the chemical solution for dissolution and deformation according to any one of claims 1 to 9 into contact with the liquid while being in a liquid state. An organic film pattern dissolution process method. The organic film pattern formed on the substrate is exposed to the vapor of the chemical solution for dissolution and deformation according to any one of claims 1 to 9, whereby the organic film pattern is dissolved and deformed. A film pattern dissolution processing method. 14. The method for dissolving and deforming an organic film pattern according to claim 13, wherein vapor generated by bubbling the chemical solution for dissolution and deformation using an inert gas is exposed to the organic film pattern. After the dissolution and deformation treatment method according to any one of claims 12 to 14, a treatment for dissolving and deforming the organic film pattern is performed again using a dissolution and deformation chemical that does not contain an alkali component. A method for dissolving and deforming an organic film pattern. The organic solvent according to claim 15, wherein the chemical solution for dissolution and deformation not containing an alkali component is a solvent containing at least one of the organic solvents shown in the following (1) to (7). A film pattern dissolution processing method.
(1) Alcohols (2) Ethers (3) Esters (4) Ketones (5) Glycol ethers (6) Nitriles (7) Amides The solution for dissolution and deformation not containing the alkali component contains at least one of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl isobutyl ketone, acetonitrile, and N, N-dimethylacetamide. Item 16. A method for dissolving and deforming an organic film pattern according to Item 15.