JP5224228B2 - Substrate processing method using chemicals - Google Patents

Description

  The present invention relates to a substrate processing method performed on a semiconductor substrate, a liquid crystal substrate, or other substrates, and a chemical solution used therefor.

  Conventionally, after forming an organic film pattern on a semiconductor wafer, liquid crystal substrate, or other substrate, a wiring film or the like is formed by pattern processing (substrate film processing) of the base film, that is, the substrate, by etching using the organic film pattern as a mask. There is technology to do.

  In general, after the base film processing, the organic film pattern is removed by a peeling process.

  However, for example, as shown in Patent Document 1, after an organic film pattern (described as a resist pattern in Patent Document 1) is formed on a substrate, the base film (one layer, (Or two layers) is subjected to pattern processing (base film processing) and re-developed (hereinafter referred to as re-development), and again using the organic film pattern as a new pattern by over-development or deformation, There is a technique for forming a wiring film having a high resistance to breakdown by forming a base film pattern into a taper shape or a step shape by pattern processing (reprocessing the base film) of one layer or two layers. In this case, the organic film pattern is removed by a peeling process after the base film is reprocessed.

  In addition, as a substrate processing method for processing a similar organic film pattern, there is a technique disclosed in Patent Document 2.

  Further, the processing of the organic film pattern may be performed by adding a melt deformation process as shown in Patent Document 3. In this organic film pattern dissolution and deformation treatment, the organic film pattern is dissolved and reflowed by bringing an organic solvent into contact with the organic film pattern (especially positive type, resist pattern) (mainly by exposure to an organic solvent gas atmosphere). I am letting.

  More specifically, the organic film pattern development described in Patent Document 1, the base film processing step by etching, the redevelopment of the organic film pattern (resist pattern), and the base film reprocessing step are more specifically described. As shown in FIG.

As shown in FIG. 7, in Patent Document 1, an organic film (photoresist in this example) 103 is applied on a substrate 101 on which a conductive film 102 is formed (FIG. 7A), and then normal exposure is performed. The initial organic film pattern 104 is formed on the substrate 101 by performing the processing, the development processing, and the heat treatment as pre-bake in this order (FIG. 7B). Subsequently, using the organic film pattern 104 as a mask, an etching process (undercoat film processing) is performed on the conductive film 102 on the substrate 101 to perform primary processing of the conductive film pattern (FIG. 7C). Thereafter, after performing a re-development process that is a re-development to the same organic film pattern, a heat process that is a pre-bake is performed again to process the organic film pattern 104 into a new pattern shape ( FIG. 7D). Further, in Patent Document 1, the conductive film 102 is etched (underwork film reworking) so that the film thickness of the conductive film 102 is reduced to about half again using the newly developed organic film pattern 104 developed again as a mask. Describes a technique for preventing the cross-sectional shape from becoming vertical or reverse taper. Note that the organic film pattern 104 is peeled off as shown in FIG.
JP-A-8-23103 JP 2005-159294 A JP 2005-159292 A

  However, in Patent Document 1, an initial organic film pattern is formed by etching processing (processing between FIG. 7B and FIG. 7C: base film processing) for the conductive film 102 on the substrate 101. However, there is no description that any one or both of the altered layer and the deposited layer are formed on the organic film pattern.

  As described above, the altered layer or the deposited layer (hereinafter referred to as an inhibition layer) formed on the surface of the organic film pattern is subjected to the next development (re-development processing: FIG. 7C) and FIG. ) During the development process. For this reason, this re-development process cannot normally be performed smoothly.

  The progress of the redevelopment process varies depending on the state of the inhibition layer. When the etching process between FIG. 7B and FIG. 7C is wet etching, the chemical solution used and the processing temperature greatly affect the state of the inhibition layer. On the other hand, in the case of dry etching, the type of gas used, the processing pressure and the discharge method are affected. The chemical damage to the organic film pattern varies depending on the type of gas used, and the magnitude of the physical impact force of the ionized gas or radical gas on the organic film pattern varies depending on the processing pressure and the discharge method. However, generally, wet etching has less physical impact force, so damage is small and development inhibition of the inhibition layer is also small.

  Thus, if the redevelopment process cannot be performed smoothly due to the presence of the inhibition layer, the redevelopment process for the organic film pattern becomes non-uniform. ) Becomes non-uniform.

  The present invention has been made to solve the above-described problems. For example, a substrate processing method capable of smoothly performing the second and subsequent development processing on an organic film pattern and a chemical solution used therefor are provided. The purpose is to provide.

  In addition, after forming an organic film pattern on a semiconductor substrate, a liquid crystal substrate, or another substrate, there may be a case where only the organic film pattern is processed again and used as it is (when the base film processing is not performed). For example, when the organic film pattern is made of an insulating material, the organic film pattern is used as the insulating film pattern.

  In order to solve the above problems, the chemical solution of the present invention has an organic film pattern formed on a substrate, and a surface of the organic film pattern on which a surface layer portion of the organic film pattern is denatured, and the organic layer A chemical solution used in a removal process for removing at least the inhibitory layer when an inhibitory layer consisting of at least one of a deposited layer formed by depositing a deposit on the surface of the film pattern is formed. And an aqueous solution containing a first component composed of at least one of a hydroxylamine derivative and a hydrazine derivative and a developing functional liquid component.

  Further, the chemical solution of the present invention has an organic film pattern formed on a substrate, a modified layer formed by altering a surface layer portion of the organic film pattern on the surface of the organic film pattern, and a surface of the organic film pattern. And a removal process for removing at least the inhibition layer, and a main process for processing the organic film pattern when an inhibition layer comprising at least one of the deposition layer formed by depositing the deposit on the substrate is formed. , In this order, a chemical solution used for the removal treatment, which is an aqueous solution containing a first component composed of at least one of a hydroxylamine derivative and a hydrazine derivative, and a developing functional solution component. It is characterized by.

  In the chemical solution of the present invention, the main process is preferably a process for removing all of the organic film pattern.

  In this case, it is preferable that the organic film pattern is a photosensitive organic film, and the chemical solution is a chemical solution used for the removal treatment performed at least after the organic film pattern is exposed.

The hydroxylamine derivative in the chemical solution of the present invention is a compound represented by [(R _1- ) (R _2- )] NOH (where R ₁ and R ₂ are C1 to C4 alkyl or hydroxyalkyl). In particular, at least one of hydroxylamine and N, N-diethylhydroxylamine is preferable.

In addition, the hydrazine derivative in the chemical solution of the present invention is [(R _1- ) (R _2- )] NN [(-R ₃ ) (-R ₄ )] (where R ₁ , R ₂ , R ₃ , R ₄ is a compound represented by any one of hydrogen, methyl, ethyl, and phenyl), and is particularly composed of at least one of hydrazine, methyl hydrazine, 1,1-dimethylhydrazine, and phenylhydrazine. It is preferable.

  In addition, the developing functional liquid component in the chemical solution of the present invention is preferably composed of at least one of tetraalkylammonium hydroxide, alkali metal hydroxide, and alkali metal carbonate.

The tetraalkylammonium hydroxide constituting the developing functional liquid component is [(R ₁ −) (R ₂ −) (R ₃ −) (R ₄ −)] N ⁺ OH ⁻ (where R ₁ , R ₂ , R ₃ and R ₄ are compounds represented by C1 to C4 alkyl or hydroxyalkyl), particularly tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, and dimethylbis (2-hydroxyethyl) ammonium hydroxide. It is preferable to consist of at least one of them.

  Moreover, it is preferable that the alkali metal hydroxide which comprises a developing function liquid component consists of at least any one of sodium hydroxide and potassium hydroxide.

  Moreover, it is preferable that the alkali metal carbonate which comprises a developing function liquid component consists of at least any one of sodium carbonate, sodium hydrogencarbonate, potassium carbonate, and potassium hydrogencarbonate.

  It is preferable that content of the said 1st component in the chemical | medical solution of this invention is 0.5 to 30 weight%. When the content of the first component is less than 0.5% by weight or more than 30% by weight, a portion other than the deteriorated layer in the organic film pattern may be removed.

  Moreover, it is preferable that content of the said developing functional liquid component in the chemical | medical solution of this invention is 0.2 weight%-10 weight%. When the content of the developing functional liquid component is less than 0.2% by weight, the effect of removing the inhibition layer formed on the surface of the organic film pattern is not exhibited. The part may be removed.

More specifically, for example, in the chemical solution of the present invention, the hydroxylamine derivative is [(R _1- ) (R _2- )] NOH (where R ₁ and R ₂ are alkyls of C1 to C4). Or hydroxyalkyl), hydroxylamine, and at least one of N, N-diethylhydroxylamine, and the hydrazine derivative is [(R _1- ) (R _2- )] NN [(- R ₃ ) (— R ₄ )] (where R ₁ , R ₂ , R ₃ , R ₄ are any one of hydrogen, methyl, ethyl and phenyl), hydrazine, methyl hydrazine, 1,1-dimethyl It contains at least one of hydrazine and phenylhydrazine, and the content of the hydroxylamine derivative and / or hydrazine derivative in the chemical solution is 0.5. It is preferable that it is 30 to 30 weight%.

Alternatively, in the chemical solution of the present invention, the developing functional solution component contains at least one of tetraalkylammonium hydroxide, alkali metal hydroxide, and alkali metal carbonate, alkyl _{ammonium, [(R 1 -) (} R 2 -) (R 3 -) (R 4 -)] N + OH - ( _{wherein, R 1, R 2, R} 3, R 4 are, C1 to C4 Or containing at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, and dimethylbis (2-hydroxyethyl) ammonium hydroxide. And the alkali metal hydroxide contains at least one of sodium hydroxide and potassium hydroxide. The alkali metal carbonate contains at least one of sodium carbonate, sodium hydrogen carbonate, potassium carbonate, and potassium hydrogen carbonate, and contains the functional component of development in the chemical solution. The amount is preferably 0.2% to 10% by weight.

Alternatively, in the chemical solution of the present invention, the hydroxylamine derivative is [(R _1- ) (R _2- )] NOH (wherein R ₁ and R ₂ are C1 to C4 alkyl or hydroxyalkyl), hydroxyl Containing at least one of an amine and N, N-diethylhydroxylamine, wherein the hydrazine derivative is [(R _1- ) (R _2- )] NN [(-R ₃ ) (-R ₄ )] (wherein R ₁ , R ₂ , R ₃ and R ₄ are any one of hydrogen, methyl, ethyl and phenyl), hydrazine, methyl hydrazine, 1,1-dimethylhydrazine and phenyl hydrazine And the content of the hydroxylamine derivative and / or hydrazine derivative in the chemical solution is 0.5 wt% to 30 wt%. %, And the developer component contains at least one of tetraalkylammonium hydroxide, alkali metal hydroxide, and alkali metal carbonate, and the tetraalkylammonium hydroxide is [ _{(R 1 -) (R 2} -) (R 3 -) (R 4 -)] N + OH - ( _{wherein, R 1, R 2, R} 3, R 4 are, from C1 C4 alkyl or hydroxyalkyl Or contains at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, and dimethylbis (2-hydroxyethyl) ammonium hydroxide, and the alkali The metal hydroxide contains at least one of sodium hydroxide and potassium hydroxide, and the alkali The metal carbonate contains at least one of sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate, and the content of the developing functional solution component in the chemical solution is 0.2. It is preferable that it is 10 to 10 weight%.

  The removal treatment is preferably a treatment of washing the substrate with a chemical solution that removes only the inhibition layer formed on the surface of the organic film pattern without removing the portions other than the altered layer in the organic film pattern. If the dissolution rate of the portion other than the altered layer in the organic film pattern is 1000 Å / min or less, more preferably 100 Å / min or less, and even more preferably 50 Å / min or less, a sufficient amount of organic film is obtained after the removal treatment. Since the pattern remains, the organic film pattern can be reprocessed suitably.

  Furthermore, the ratio V1 / V2 between the speed V1 for dissolving the inhibition layer and the speed V2 for dissolving the portion other than the altered layer in the organic film pattern by the chemical solution of the present invention is 0.5 or more (for example, 1000 or less) And preferably 5.0 or less.

  Specifically, for example, the ratio V1 / V2 between the speed V1 for dissolving the inhibitory layer and the speed V2 for dissolving a portion other than the altered layer in the organic film pattern is 0.5 or more ( As an example, it is preferably 1000 or less), and the rate at which the portion other than the deteriorated layer in the organic film pattern is dissolved is preferably 1000 kg / min or less.

  Alternatively, the ratio V1 / V2 between the speed V1 for dissolving the inhibition layer and the speed V2 for dissolving the portion other than the altered layer in the organic film pattern by the chemical solution of the present invention is 0.5 or more (for example, 1000 or less) More preferably, the rate of dissolving the portion other than the deteriorated layer in the organic film pattern is 100 kg / min or less.

  Alternatively, the ratio V1 / V2 between the speed V1 for dissolving the inhibition layer and the speed V2 for dissolving the portion other than the altered layer in the organic film pattern with the chemical solution of the present invention is 0.5 (for example, 1000 or less). More preferably, the rate of dissolving the portion other than the deteriorated layer in the organic film pattern is 50 kg / min or less.

  The deteriorated layer is, for example, one in which the surface layer portion of the organic film pattern has deteriorated due to at least one of the following factors: time degradation, thermal oxidation, and thermosetting.

  Alternatively, the altered layer is, for example, one in which the surface layer portion of the organic film pattern has been altered by wet etching treatment.

  Alternatively, the altered layer is, for example, one in which the surface layer portion of the organic film pattern is altered by dry etching or ashing.

  The deposited layer is, for example, a layer deposited on the surface of the organic film pattern by deposition by dry etching. Alternatively, the altered layer is a layer in which the surface layer portion of the organic film pattern has been altered due to deposition by dry etching.

  The initial organic film pattern formed on the substrate may be, for example, an organic film pattern formed by a printing method, or the initial organic film pattern formed on the substrate may be photolithography. It may be an organic film pattern formed by a method.

  The organic film pattern is preferably made of a photosensitive organic film, for example.

  In this case, the photosensitive organic film is a positive photosensitive organic film or a negative photosensitive organic film.

  The positive photosensitive organic film is preferably composed mainly of, for example, a novolac resin.

  It is also preferred that the photosensitive organic film becomes alkali-soluble when exposed to light.

  The chemical solution of the present invention is preferably a chemical solution having an organic film pattern developing function.

  Or the tetraalkyl ammonium hydroxide in the chemical | medical solution of this invention contains the component which has the development function of an organic film pattern, for example.

  The substrate is preferably a semiconductor substrate or a substrate constituting a display device, for example.

  In the substrate processing method of the present invention, an organic film pattern is formed on a substrate, and the surface of the organic film pattern has an altered layer obtained by altering a surface layer portion of the organic film pattern, and the organic film pattern In the substrate processing method for performing a removal process for removing at least the inhibition layer when an inhibition layer comprising at least one of a deposition layer formed by depositing deposits on the surface is formed, the removal process Is performed using the chemical solution of the present invention.

  In the substrate processing method of the present invention, an organic film pattern is formed on a substrate, and the surface of the organic film pattern has an altered layer obtained by altering a surface layer portion of the organic film pattern, and the organic film pattern When an inhibition layer consisting of at least one of a deposition layer formed by depositing deposits on the surface is formed, a removal process for removing at least the inhibition layer, and a book for processing the organic film pattern In the substrate processing method in which the processing is performed in this order, the removal processing is performed using the chemical solution of the present invention.

  In the present process, it is preferable that at least a part of the organic film pattern is reduced or at least a part of the organic film pattern is removed.

  Alternatively, in the present process, it is also preferable to reduce all of the organic film pattern or remove all of the organic film pattern.

  The main treatment is preferably performed using a stripping solution or a chemical solution having a developing function (may be a commercially available developing solution).

  In the substrate processing method of the present invention, a first base film processing step of patterning a base film of the organic film pattern by etching using the organic film pattern as a mask before the removing process, and the base film processing step It is a preferable example to include a second base film processing step of patterning the base film again using the later organic film pattern or the organic film pattern processed by the main processing as a mask. .

  In this case, it is preferable that the pattern of the base film is processed into a taper shape or a step shape by the second base film processing step.

  The substrate processing method of the present invention further includes an organic film pattern processing for processing the organic film pattern after at least one of the removal processing and the main processing, and the organic film pattern processing The treatment is also preferably performed by a dissolution / deformation process in which the organic film pattern is dissolved and deformed.

  The substrate processing method of the present invention further includes an organic film pattern processing for processing the organic film pattern after at least one of the removal processing and the main processing, and the organic film pattern processing In the treatment, it is also preferable to perform a heat treatment for heating the organic film pattern and a dissolution deformation treatment for dissolving and deforming the organic film pattern in this order.

  In the substrate processing method of the present invention, before the organic film pattern processing, at least one of exposure processing, development processing, wet etching processing, and dry etching processing is performed on the organic film pattern. It is preferable to carry out.

  The substrate processing method of the present invention preferably further includes a base film processing step of patterning the base film of the organic film pattern using the organic film pattern before deformation by the dissolution deformation process as a mask.

  Furthermore, the substrate processing method of the present invention preferably further comprises a base film processing step of patterning the base film of the organic film pattern using the organic film pattern after the deformation by the dissolution deformation process as a mask.

  It is a preferable example that the dissolution deformation process is a process of expanding the area of the organic film pattern.

  The dissolution deformation process is preferably a process of mutually integrating adjacent organic film patterns.

  The dissolution deformation process is preferably a process for flattening the organic film pattern.

  It is also preferable that the dissolution deformation process is a process of deforming the organic film pattern so as to become an insulating film covering a circuit pattern formed on the substrate.

  The dissolution deformation process is preferably a process of dissolving and reflowing the organic film pattern using an organic solution.

  In this case, the organic solution is preferably a solution containing at least one of organic solvents shown in the following (1) to (5).

(1) Alcohols (R-OH)
(2) Ethers (R—O—R, Ar—O—R, Ar—O—Ar)
(3) Esters (4) Ketones (5) Glycol ethers (However, in (1) and (2), R represents an alkyl group or a substituted alkyl group, and Ar represents a phenyl group or an aromatic ring other than a phenyl group. )
The dissolution reflow is preferably performed by bringing the organic solution into contact with the organic film pattern.

  In this case, the dissolution reflow may be performed by immersing the organic film pattern in the organic solution.

  Alternatively, the dissolution reflow is preferably performed by exposing the organic film pattern to the vapor of the organic solution.

  Alternatively, the dissolution deformation treatment is preferably a gas atmosphere treatment performed by exposing the organic film pattern to a gas atmosphere obtained by gasifying the organic solution.

  In this case, the gas atmosphere is preferably obtained by bubbling the organic solvent using an inert gas.

  Here, the initial organic film pattern formed on the substrate may be formed with a uniform film thickness as a whole, but is an organic film pattern formed with a film thickness of at least two stages. May be.

  An organic film pattern having a film thickness of two or more steps can be obtained by making the exposure amounts of the organic film different from each other.

  That is, in order to form an organic film pattern having a film thickness of two or more stages, it is preferable to control the exposure amount in the initial exposure for forming the organic film pattern to two or more stages in the plane of the organic film pattern. . Specifically, for example, a reticle mask having two or more kinds of transmitted light amounts may be used in the initial exposure. As described above, by performing the development process (the development process for forming the original organic film pattern, which is different from the development process performed as the main process) after controlling the exposure amount to two or more steps, If it is a resist, the organic film of only a portion with a large exposure amount or a negative type resist is thinned preferentially, so an organic film pattern having two or more stages of film thickness is formed. Can do.

  Here, since the history of exposure by the initial exposure remains after that, by performing the development processing of this processing, the thin film portion having a small thickness in the organic film pattern is selectively further thinned, or the organic film A thin film portion having a small film thickness in the pattern can be selectively removed.

  In addition, as the developing functional liquid used in the development processing of this processing, if the developing functional liquid used in the developing processing for forming the original organic film pattern is positive, the same positive developing functional liquid is used. If the developing functional liquid used in the development processing for forming the original organic film pattern is negative, it is preferable to use the negative developing functional liquid.

  Here, this process of selectively thinning or removing the thin film portion is a state in which the organic film pattern is not exposed until the organic film pattern processing is performed after the initial organic film pattern is formed on the substrate. It can carry out suitably by keeping to.

  In these cases, a base film processing step of patterning the base film of the organic film pattern using the organic film pattern as a mask, and a relatively thin organic film among the plurality of organic film patterns having different film thicknesses. A thick film organic film pattern remaining step of removing the film pattern and leaving an organic film pattern thicker than the relatively thin organic film pattern.

  In this case, it is a preferable example to further include a second base film processing step of patterning the base film using the organic film pattern remaining after the thick film organic film pattern residual step as a mask.

  In addition, the organic film by the exposure process in the organic film pattern processing process is formed by maintaining the organic film pattern in a non-photosensitive state until the organic film pattern processing process after the initial formation of the organic film pattern on the substrate. It is possible to suitably determine a new pattern shape of the pattern.

  In the substrate processing method of the present invention, in the removal process, it is a preferable example that the inhibition layer is selectively removed.

  In the substrate processing method of the present invention, it is also preferable that the removal process removes the inhibition layer and exposes and leaves portions other than the altered layer in the organic film pattern.

  The substrate processing method of the present invention preferably includes a base film processing step of patterning the base film of the organic film pattern by etching using the organic film pattern as a mask before the removing process.

  Further, the removal process is performed following the exposure process for the organic film pattern (exposure process different from the initial exposure for the organic film), the exposure process is performed during the removal process, or the exposure process is removed. It is also preferable to carry out between the processing and the main processing.

  Here, it is preferable to perform this exposure process only on the organic film pattern included in the desired range (front surface or part) of the substrate among the organic film patterns.

  This exposure process may be an exposure process for the purpose of performing sufficient exposure on the entire surface of the substrate, or is performed to determine a new pattern shape of the organic film pattern depending on the exposure range by the exposure process. It may be processing.

  When determining a new pattern shape of the organic film pattern according to the exposure range by the exposure process, for example, the exposure process may be performed by setting the exposure range so as to separate at least one of the organic film patterns into a plurality of portions. Can be mentioned.

  In the present invention, after an organic film pattern is formed on a semiconductor wafer, a liquid crystal substrate, or another substrate, the organic film pattern is only processed again and used as it is (when the base film processing is not performed). For example, when the organic film pattern is made of an insulating material, the organic film pattern is used as the insulating film pattern.

  The chemical solution may contain additives such as anticorrosives and stabilizers as necessary.

  The manufacturing method of the present invention is characterized by manufacturing a display device having a substrate or a semiconductor device having a substrate using the substrate processing method of the present invention.

  In a preferred example, the display device is a liquid crystal display device, an EL display device, a field emission display device, or a plasma display device.

  According to the present invention, since the removal process for removing the inhibition layer formed on the surface of the organic film pattern is provided without dissolving the organic film pattern, for example, the second and subsequent development processes on the organic film pattern can be smoothly performed. It can be performed, or the main process of processing the organic film pattern after the removal process can be performed smoothly.

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

[First Embodiment]
FIG. 1 is a diagram showing a series of steps in the substrate processing method according to the first embodiment.

  In the prior art shown in FIG. 7, redevelopment processing is performed between FIG. 7C and FIG. 7D, but in the substrate processing method according to this embodiment, between FIG. 1C and FIG. 7 is different from the prior art shown in FIG. 7 in that the removal process and the redevelopment process are performed.

  Details will be described below.

  First, as shown in FIG. 1A, an organic film 3 is applied on a substrate 1 on which a conductive film 2 is formed.

  Next, the normal organic film pattern 4 is formed on the substrate 1 by performing a normal exposure process, a development process, and a heating process as a pre-bake in this order (FIG. 1B).

  Subsequently, the conductive film 2 is primarily patterned by performing an etching process on the conductive film 2 on the substrate 1 using the original organic film pattern 4 as a mask (underlying film processing step, first The base film processing step). That is, a portion of the conductive film 2 that is not covered with the organic film pattern 4 is removed by etching (wet etching or dry etching), thereby obtaining the state shown in FIG.

  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 deposits on the surface of the organic film pattern, The inhibition layer which consists of at least one of these is formed.

  Subsequently, the organic film pattern 4 is subjected to a removal process using the chemical solution according to the present embodiment to selectively remove the inhibition layer, thereby exposing and exposing portions other than the altered layer in the organic film pattern 4. After the remaining, a re-development process is performed, and then a heat treatment that is a pre-bake is performed again, thereby performing a main process for processing the original organic film pattern 4 into an organic film pattern 5 having a new pattern shape. Do. That is, the organic film pattern 4 is processed so that the planar existence range on the conductive film 2 is reduced to form the organic film pattern 5 (FIG. 1D).

  Thus, in this process, for example, a part of the organic film pattern 4 is removed (or it can be said that all of the organic film pattern 4 is reduced).

  Furthermore, using the new organic film pattern 5 as a mask, etching (wet etching or dry etching) is performed so that a portion of the conductive film 2 that is not covered with the organic film pattern 5 is thinned (for example, about half the film thickness). Etching) makes the cross-sectional shape of the conductive film 2 stepped (second base film processing step) (FIG. 1E).

  Thereafter, the organic film pattern 5 is peeled and removed (FIG. 1F).

  Thus, by making the cross-sectional shape of the conductive film 2 stepped, it is possible to prevent the cross-section of the conductive film 2 from being vertical or inversely tapered.

  Next, the chemical | medical solution used for a removal process is demonstrated.

  The chemical solution according to the present embodiment used for the removal treatment is an aqueous solution containing a first component composed of at least one of a hydroxylamine derivative and a hydrazine derivative and a developing functional solution component.

The hydroxylamine derivative in the chemical solution according to this embodiment is a compound represented by [(R _1- ) (R _2- )] NOH (where R ₁ and R ₂ are C1 to C4 alkyl or hydroxyalkyl). In particular, it is preferably at least one of hydroxylamine and N, N-diethylhydroxylamine.

In addition, the hydrazine derivative in the chemical solution according to the present embodiment is [(R _1- ) (R _2- )] NN [(-R ₃ ) (-R ₄ )] (where R ₁ , R ₂ , R ₃ , R ₄ is a compound represented by any one of hydrogen, methyl, ethyl and phenyl), and in particular, at least one of hydrazine, methyl hydrazine, 1,1-dimethylhydrazine and phenylhydrazine. Preferably it consists of.

  Further, the developing functional liquid component in the chemical solution according to the present embodiment is preferably composed of at least one of tetraalkylammonium hydroxide, alkali metal hydroxide, and alkali metal carbonate.

The tetraalkylammonium hydroxide constituting the developing functional liquid component is [(R ₁ −) (R ₂ −) (R ₃ −) (R ₄ −)] N ⁺ OH ⁻ (where R ₁ , R ₂ , R ₃ and R ₄ are compounds represented by C1 to C4 alkyl or hydroxyalkyl), particularly tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, and dimethylbis (2-hydroxyethyl) ammonium hydroxide. It is preferable to consist of at least one of them.

  Moreover, it is preferable that the alkali metal hydroxide which comprises a developing function liquid component consists of at least any one of sodium hydroxide and potassium hydroxide.

  Moreover, it is preferable that the alkali metal carbonate which comprises a developing function liquid component consists of at least any one of sodium carbonate, sodium hydrogencarbonate, potassium carbonate, and potassium hydrogencarbonate.

  It is preferable that content of the said 1st component in the chemical | medical solution which concerns on this embodiment is 0.5 to 30 weight%. When the content of the first component is less than 0.5% by weight or more than 30% by weight, a portion other than the deteriorated layer in the organic film pattern may be removed.

  In addition, the content of the developing functional liquid component in the chemical solution according to the present embodiment is preferably 0.2% by weight to 10% by weight. When the content of the developing functional liquid component is less than 0.2% by weight, the effect of removing the inhibition layer formed on the surface of the organic film pattern is not exhibited. The part may be removed.

More specifically, for example, in the chemical solution according to the present embodiment, the hydroxylamine derivative is [(R _1- ) (R _2- )] NOH (where R ₁ and R ₂ are C1 to C4). Or at least one of N, N-diethylhydroxylamine, and the hydrazine derivative is [(R _1- ) (R _2- )] NN [ (—R ₃ ) (— R ₄ )] (where R ₁ , R ₂ , R ₃ and R ₄ are any one of hydrogen, methyl, ethyl and phenyl), hydrazine, methyl hydrazine, 1,1 -Content of hydroxylamine derivative and / or hydrazine derivative in the chemical solution containing at least one of dimethylhydrazine and phenylhydrazine Is preferably 0.5 wt% to 30 wt%.

Alternatively, in the chemical solution according to the present embodiment, the developing functional liquid component contains at least one of tetraalkylammonium hydroxide, alkali metal hydroxide, and alkali metal carbonate, and the water oxide _{tetraalkylammonium, [(R 1 -) (} R 2 -) (R 3 -) (R 4 -)] N + OH - ( _{wherein, R 1, R 2, R} 3, R 4 are, C1 To C4 alkyl or hydroxyalkyl) or at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, and dimethylbis (2-hydroxyethyl) ammonium hydroxide. The alkali metal hydroxide contains at least one of sodium hydroxide and potassium hydroxide. And the alkali metal carbonate contains at least one of sodium carbonate, sodium hydrogen carbonate, potassium carbonate, and potassium hydrogen carbonate, and a developing functional liquid component in the chemical solution The content of is preferably 0.2% by weight to 10% by weight.

Alternatively, in the chemical solution according to this embodiment, the hydroxylamine derivative is [(R _1- ) (R _2- )] NOH (where R ₁ and R ₂ are C1 to C4 alkyl or hydroxyalkyl). , Hydroxylamine, and N, N-diethylhydroxylamine, wherein the hydrazine derivative is [(R _1- ) (R _2- )] NN [(-R ₃ ) ( -R _{4)] (wherein, R 1, R 2, R} 3, R 4 is hydrogen, methyl, one of ethyl and phenyl), hydrazine, methylhydrazine, 1,1-dimethylhydrazine, and, Containing at least one of phenylhydrazine, and the content of the hydroxylamine derivative and / or hydrazine derivative in the chemical solution is 0.5 wt% to 30% by weight, and the developer component contains at least one of tetraalkylammonium hydroxide, alkali metal hydroxide, and alkali metal carbonate, and the tetraalkylammonium hydroxide contains _{, [(R 1 -) (} R 2 -) (R 3 -) (R 4 -)] N + OH - ( _{wherein, R 1, R 2, R} 3, R 4 are, from C1 C4 alkyl or Hydroxyalkyl), or containing at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, and dimethylbis (2-hydroxyethyl) ammonium hydroxide, The alkali metal hydroxide contains at least one of sodium hydroxide and potassium hydroxide, The alkali metal carbonate contains at least one of sodium carbonate, sodium hydrogen carbonate, potassium carbonate, and potassium hydrogen carbonate, and the content of the developing functional liquid component in the chemical solution is 0.00. It is preferable that it is 2 to 10 weight%.

  If the dissolution rate of the portion other than the altered layer in the organic film pattern 4 is 1000 Å / min or less, more preferably 100 ｍｉｎ / min or less, and even more preferably 50 以下 / min or less, a sufficient amount of organic after the removal treatment is performed. Since the film pattern 4 remains, the organic film pattern 4 can be suitably reprocessed.

  Furthermore, the ratio V1 / V2 between the speed V1 for dissolving the deteriorated layer (or the inhibition layer) in the organic film pattern 4 and the speed V2 for dissolving the portion other than the deteriorated layer is 0.5 or more by the chemical solution according to the present embodiment. (For example, 1000 or less), preferably 5.0 or less.

  Specifically, for example, the ratio V1 / V2 between the speed V1 for dissolving the inhibition layer and the speed V2 for dissolving a portion other than the altered layer in the organic film pattern is 0.5 by the chemical solution according to the present embodiment. It is preferable that the above is (for example, 1000 or less), and the rate at which the portion other than the deteriorated layer in the organic film pattern is dissolved is 1000 kg / min or less.

  Alternatively, the ratio V1 / V2 between the speed V1 for dissolving the inhibition layer and the speed V2 for dissolving a portion other than the altered layer in the organic film pattern is 0.5 or more (for example, More preferably, the rate of dissolving portions other than the deteriorated layer in the organic film pattern is 100 kg / min or less.

  Alternatively, the ratio V1 / V2 between the speed V1 for dissolving the inhibition layer and the speed V2 for dissolving the portion other than the altered layer in the organic film pattern by the chemical solution according to the present embodiment is 0.5 (for example, 1000 It is more preferable that the rate of dissolving the portion other than the deteriorated layer in the organic film pattern is 50 kg / min or less.

  The chemical solution according to the present embodiment preferably has a function of developing the organic film pattern 4.

  The tetraalkylammonium hydroxide in the chemical solution according to the present embodiment preferably contains a component having a developing function for the organic film pattern 4.

  Next, the inhibition layer formed on the surface of the organic film pattern 4 at the stage of FIG.

  The inhibition layer inhibits the redevelopment process, and as described above, the alteration layer formed by altering the surface portion of the organic film pattern 4 and the deposits are deposited on the surface of the organic film pattern. And at least one of a deposited layer.

  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. Further, when the inhibition layer includes a deposition layer, the deposition layer is, for example, a layer deposited on the surface of the organic film pattern 4 by deposition by dry etching.

  According to the first embodiment as described above, by performing the removal process, it is possible to facilitate the penetration of the developing functional liquid into the organic film pattern 4 in the subsequent redevelopment process in the main process, and the effect of the development process. Can be made uniform. The same effect can be obtained when this treatment is performed by a chemical treatment using a chemical solution that does not have the function of developing the organic film pattern 4 but has the function of dissolving and removing the organic film pattern 4.

[Second Embodiment]
FIG. 2 is a diagram showing a series of steps in the substrate processing method according to the second embodiment.

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

  First, as shown in FIG. 2A, an organic film 3 is applied on a substrate 1 on which a conductive film 2 is formed.

  Next, an exposure process in which the exposure amount is controlled in two or more stages (that is, two-time continuous exposure, halftone mask exposure using a pattern formed of a film having two or more stages of transmittance, or normal pattern and exposure) The original organic film pattern 4 having a two-stage film thickness is obtained by performing, in this order, an exposure process using a gray-tone mask with a fine pattern below the limit, a development process, and a heating process as a pre-bake. 1 is formed. Specifically, for example, as shown in FIG. 2B, an organic film pattern 4 having a thick central portion and a thin peripheral portion is formed.

  Subsequently, the conductive film 2 is primarily patterned by performing an etching process on the conductive film 2 on the substrate 1 using the original organic film pattern 4 as a mask (underlying film processing step, first The base film processing step). That is, by removing the portion of the conductive film 2 that is not covered with the organic film pattern 4 by etching (wet etching or dry etching), the state shown in FIG.

  Subsequently, by removing the inhibition layer selectively by performing a removal process using the same chemical solution as in the first embodiment on the organic film pattern 4, other than the altered layer in the organic film pattern 4. After the portion is exposed and left, a redevelopment process is performed, and then a heat treatment that is a pre-bake is performed again, whereby the original organic film pattern 4 is changed to an organic film pattern 5 having a new pattern shape. This processing is performed. That is, the thin part of the peripheral film portion in the organic film pattern 4 is removed and processed into the organic film pattern 5 having a pattern shape with only one stage (FIG. 2D).

  Thus, in this process, for example, a part of the organic film pattern 4 is removed (or, as a result of reducing the whole organic film pattern 4, a part of the organic film pattern 4 may be removed).

  Further, using the organic film pattern 5 having a new single-layer thickness as a mask, a portion of the conductive film 2 that is not covered with the organic film pattern 5 is etched (wet etching or dry etching) so that the film thickness is about half. Etching) makes the cross-sectional shape of the conductive film 2 stepped (second base film processing step) (FIG. 2E).

  Thereafter, the organic film pattern 5 is peeled and removed (FIG. 2F).

  Thus, by making the cross-sectional shape of the conductive film 2 stepped, it is possible to prevent the cross-section of the conductive film 2 from being vertical or inversely tapered.

  According to the second embodiment as described above, the same effect as in the first embodiment can be obtained.

[Third Embodiment]
FIG. 3 is a diagram showing a series of steps in the substrate processing method according to the third embodiment.

  Also in the third embodiment, an example in which the original organic film pattern 4 is formed by a photolithography method so as to have a plurality of stages (for example, two stages) of film thickness will be described.

  First, as shown in FIG. 3A, 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, an exposure process in which the exposure amount is controlled in two or more stages (that is, two-time continuous exposure, halftone mask exposure using a pattern formed of a film having two or more stages of transmittance, or normal pattern and exposure) The original organic film pattern 4 having a two-stage film thickness is obtained by performing, in this order, an exposure process using a gray-tone mask with a fine pattern below the limit, a development process, and a heating process as a pre-bake. 1 is formed. Specifically, for example, as shown in FIG. 3B, the organic film pattern 4 is formed such that the film thickness at the center is small and the film thickness at both sides is small.

  Subsequently, using the initial organic film pattern 4 as a mask, an etching process (wet etching or dry etching) on the conductive film 2 and the semiconductor film 6 on the substrate 1 is performed, so that the conductive film 2 is temporarily formed. In addition to pattern processing, the semiconductor film 6 is patterned (base film processing step, first base film processing step) (FIG. 3C). That is, portions of the conductive film 2 and the semiconductor film 6 that are not covered with the organic film pattern 4 are removed. Here, the etching process of the conductive film 2 can be performed by wet etching or dry etching, and the etching process of the semiconductor film 6 is performed by dry etching following the etching of the conductive film 2.

  Subsequently, by removing the inhibition layer selectively by performing a removal process using the same chemical solution as in the first embodiment on the organic film pattern 4, other than the altered layer in the organic film pattern 4. After the portion is exposed and left, a redevelopment process is performed, and then a heat treatment that is a pre-bake is performed again, whereby the original organic film pattern 4 is changed to an organic film pattern 5 having a new pattern shape. This processing is performed. That is, the thin part of the central portion of the organic film pattern 4 is removed, and the organic film pattern 5 is processed into a mutually separated organic film pattern 5 with a pattern shape having a single-layer thickness (FIG. 3D). . Thus, in this process, for example, a part of the organic film pattern 4 is removed (or, as a result of reducing the whole organic film pattern 4, a part of the organic film pattern 4 may be removed). In this embodiment, this step also corresponds to a thick organic film pattern remaining step.

  Further, the organic film pattern 5 is formed in the conductive film 2 by performing the second etching (wet etching or dry etching) on the conductive film 2 using the new organic film pattern 5 having a one-stage thickness as a mask. The portion not covered with 5 is removed, and the conductive film 2 is also processed into a pattern shape separated from each other (second base film processing step). That is, a part of the conductive film 2 is processed into a pattern shape different from that of the semiconductor film 6 (FIG. 3E).

  Thereafter, the organic film pattern 5 is peeled and removed (FIG. 3F).

In the third embodiment, for example, when the semiconductor film 6 is n ⁺ a-Si (high-concentration semiconductor film for ohmic connection) or a-Si (amorphous silicon film), the source / drain electrodes in the TFT substrate are used. This is a processing method that can be used to form wiring and a channel portion.

According to the third embodiment as described above, for example, when the semiconductor film 6 is n ⁺ a-Si or a-Si, when forming the source / drain electrodes, the wiring, and the channel portion in the TFT substrate, The same effect as the first embodiment is obtained.

[Fourth Embodiment]
FIG. 4 is a diagram showing a series of steps in the substrate processing method according to the fourth embodiment.

  Also in the fourth embodiment, an example in which the original organic film pattern 4 is formed by a photolithography method so as to have a plurality of stages (for example, two stages) of film thickness will be described.

  First, as shown in FIG. 4A, 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, an exposure process in which the exposure amount is controlled in two or more stages (that is, two-time continuous exposure, halftone mask exposure using a pattern formed of a film having two or more stages of transmittance, or normal pattern and exposure) Initially separated from each other by carrying out an exposure process using a gray-tone mask with a fine pattern below the limit), a development process, and a heating process as a pre-bake in this order. The organic film pattern 4 is formed on the substrate 1. Specifically, for example, as shown in FIG. 4B, 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 organic film pattern 4 The organic film pattern 4 separated from each other is formed so that the portion far from the film pattern 4 is thin.

  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 ( Base film processing step, first base film processing step). That is, the portion of the conductive film 2 that is not covered with the organic film pattern 4 is removed (FIG. 4C).

  Subsequently, by removing the inhibition layer selectively by performing a removal process using the same chemical solution as in the first embodiment on the organic film pattern 4, other than the altered layer in the organic film pattern 4. After the portion is exposed and left, a redevelopment process is performed, and then a heat treatment that is a pre-bake is performed again, whereby the original organic film pattern 4 is changed to an organic film pattern 5 having a new pattern shape. This processing is performed. That is, in each of a pair of organic film patterns 4 adjacent to each other, by removing a portion that is far from the other organic film pattern 4 and has a thin film thickness, the organic film pattern 5 is processed into a pattern shape having a film thickness of only one step. (FIG. 4D). Thus, in this process, for example, a part of the organic film pattern 4 is removed (or, as a result of reducing the whole organic film pattern 4, a part of the organic film pattern 4 may be removed). In this embodiment, this step also corresponds to a thick organic film pattern remaining step.

  Further, by reflowing the organic film pattern 5 having a film thickness of only one new stage (heating treatment or dissolving reflow treatment by exposing to an organic solvent vapor), adjacent organic film patterns 5 are mutually connected. It is integrated and processed into one new organic film pattern 7. As a result, a portion of the semiconductor film 6 located between the pair of adjacent conductive films 2 is covered with the organic film pattern 7 (see FIG. 4E).

  Subsequently, by using the new organic film pattern 7 and the conductive film 2 below as a mask, the semiconductor film 6 is etched (dry etching), thereby changing the pattern shape of the semiconductor film 6 to the pattern of the conductive film 2 (in this case, Formed in a pattern shape (in this case, an integrated pattern) different from the separation pattern in which the adjacent conductive film 2 is separated (second base film processing step, base film processing step) (FIG. 4E) .

  Thereafter, the organic film pattern 7 is peeled and removed (FIG. 4F).

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

  In each of the above embodiments, in order to redevelop the organic film pattern, all the processes before the redevelopment process such as baking and etching are performed on the organic film pattern before the redevelopment process. However, it is necessary to take care that the thermal damage to the organic film pattern is suppressed and the developing function remains. Specifically, it must be kept at a temperature lower than 150 ° C., avoiding 150 ° C. or higher where the crosslinking reaction of the organic film is promoted. It is important to keep the temperature below 140 ° C. optimally.

  However, in the case where the temperature at which crosslinking is promoted is different from this material, the temperature may be made lower than that temperature.

  Further, the original organic film pattern 4 formed on the substrate 1 is not limited to the one formed by the photolithography method, but may be one formed by the printing method.

  Moreover, it is preferable that the organic film pattern 4 consists of a photosensitive organic film, for example. In this case, the photosensitive organic film is a positive photosensitive organic film or a negative photosensitive organic film. When the organic film pattern 4 is formed of a positive photosensitive organic film, for example, it is preferable that the organic film pattern 4 is mainly composed of a novolac resin. The photosensitive organic film is also preferably one that becomes alkali-soluble when exposed to light.

  Moreover, the chemical | medical solution which concerns on this embodiment is applicable not only to the above removal processes but the process which removes all the organic film patterns 4 on the board | substrate 1. FIG. In this case, the organic film pattern 4 on the substrate 1 is a photosensitive organic film, and the chemical solution for removal treatment is preferably a chemical solution used for removal treatment performed after at least the organic film pattern 4 is exposed. .

  Further, in the present process performed after the removal process, all of the organic film pattern on the substrate 1 may be removed.

  The chemical solution used in this treatment is preferably a chemical solution having a developing function, but may be a stripping solution.

  Further, this process may be a process of reducing at least a part of the organic film pattern 4.

  Next, specific examples of chemicals used in the removal process of the substrate processing method according to each of the above embodiments will be described.

  In addition, the chemical | medical solution demonstrated below can be used not only for the substrate processing method which concerns on said embodiment but for another substrate processing method.

  In this example, by performing the experiment described below, the removal performance of the inhibition layer in the organic film pattern 4 and the residual performance of the portion other than the altered layer in the organic film pattern 4 are confirmed, and the removal process is performed. The preferred specific example of the chemical | medical solution used was derived.

  First, an etching solution containing 7% ammonium nitrate, 18% ceric ammonium nitrate, and 75% water was prepared.

  As the substrate 1, a glass substrate having a 200 nm thick Cr film as the conductive film 2 on the surface was prepared.

  An organic film 3 (novolak resin resist) is formed on the substrate 1 (for example, a state corresponding to FIG. 1A), and an organic film pattern 4 is formed by exposure, development, and pre-baking (for example, FIG. 1B )).

  Next, a time for just etching the substrate 1 on which the organic film pattern 4 is formed as described above in the above-described etching solution at 40 ° C. (the Cr film (conductive film 2) not covered with the organic film pattern 4 disappears). Etching was performed by immersing in time (for example, a state corresponding to FIG. 1C). Further, the substrate 1 was washed with water and dried.

  This board | substrate 1 was made into the process target object of the experiment demonstrated in a present Example. That is, the substrate 1 in the state in which the inhibition layer was formed on the surface of the original organic film pattern 4 was used as the processing object of the experiment.

  Next, each of the substrates 1 in the chemical solutions having the compositions shown in the respective columns of “Examples 1 to 8” and “Comparative Examples 1 to 11” in FIG. The removal treatment of Examples 1 to 8 and Comparative Examples 1 to 11 was performed by immersing at 60 ° C. for 60 seconds.

  Here, the following abbreviations in FIG. 6 mean the compounds shown to the right of each abbreviation.

HA: hydroxylamine TMAH: tetramethylammonium hydroxide TEAH: tetraethylammonium hydroxide DEHA: N, N-diethylhydroxylamine MEA: monoethanolamine BDG: diethylene glycol, monobutyl ether PW: water That is, the chemical solution of Example 1 is 5 An aqueous solution consisting of wt% hydroxylamine, 2 wt% tetramethylammonium hydroxide, and 93 wt% water.

  The chemical solution of Example 2 is composed of 0.5% by weight hydroxylamine, 2% by weight tetramethylammonium hydroxide, and 97.5% by weight (rounded off to 98 in FIG. 6). It is an aqueous solution.

  The chemical solution of Example 3 is an aqueous solution composed of 30% by weight hydroxylamine, 10% by weight tetramethylammonium hydroxide, and 60% by weight water.

  The chemical solution of Example 4 is composed of 5% by weight of hydroxylamine, 0.5% by weight of tetramethylammonium hydroxide, and 94.5% by weight of water (rounded up to 95 in FIG. 6). It is an aqueous solution.

  The chemical solution of Example 5 is an aqueous solution composed of 5% by weight hydroxylamine, 2% by weight tetramethylammonium hydroxide, and 93% by weight water.

  The chemical solution of Example 6 is an aqueous solution composed of 5% by weight hydroxylamine, 2% by weight choline, and 93% by weight water.

  The chemical solution of Example 7 is an aqueous solution composed of 5% by weight of N, N-diethylhydroxylamine, 2% by weight of tetramethylammonium hydroxide, and 93% by weight of water.

  The chemical solution of Example 8 is an aqueous solution composed of 5% by weight of hydrazine, 2% by weight of tetramethylammonium hydroxide, and 93% by weight of water.

  The chemical solution of Comparative Example 1 is a 2.38 wt% tetramethylammonium hydroxide aqueous solution (rounded to the nearest 2.4 in FIG. 6).

  The chemical solution of Comparative Example 2 is a 20% by weight tetramethylammonium hydroxide aqueous solution.

  The chemical solution of Comparative Example 3 is a 5% by weight hydroxylamine aqueous solution.

  The chemical solution of Comparative Example 4 is composed of 20% by weight monoethanolamine, 60% by weight organic solvent (diethylene glycol and monobutyl ether), and 20% by weight water.

  The chemical solution of Comparative Example 5 is composed of 40% by weight of monoethanolamine and 60% by weight of an organic solvent (diethylene glycol and monobutyl ether).

  The chemical solution of Comparative Example 6 consists only of organic solvents (diethylene glycol and monobutyl ether).

  The chemical solution of Comparative Example 7 is composed of 5% by weight hydroxylamine, 5% by weight organic solvent (diethylene glycol and monobutyl ether), and 90% by weight water.

  The chemical solution of Comparative Example 8 is composed of 5% by weight hydroxylamine, 15% by weight tetramethylammonium hydroxide, and 80% by weight water.

  The chemical solution of Comparative Example 9 is composed of 5% by weight hydroxylamine, 0.1% by weight tetramethylammonium hydroxide, and 94.9% by weight (rounded to the nearest 95) in FIG. .

  The chemical solution of Comparative Example 10 is composed of 40% by weight hydroxylamine, 2% by weight tetramethylammonium hydroxide, and 58% by weight water.

  The chemical solution of Comparative Example 11 was composed of 0.2% by weight hydroxylamine, 2% by weight tetramethylammonium hydroxide, and 97.8% by weight (rounded to 98 in FIG. 6). .

After performing the removal process using the chemical solutions of Examples 1 to 8 and Comparative Examples 1 to 11 for the target substrate 1, each of the substrates 1 is washed with pure water, and an air gun that blows out N ₂ gas. Then, pure water was blown off from the substrate 1 and dried naturally.

  At this stage, the remaining state of the organic film pattern 4 on each substrate 1 was observed with an optical microscope, and changes in the organic film pattern 4 were examined.

  The results are shown in the column “After chemical treatment” in FIG. Judgment criteria are as follows.

  ○: The organic film pattern is almost unchanged.

  Δ: Parts other than the altered layer in the organic film pattern are removed, but the altered layer remains. Alternatively, the organic film pattern is dissolved non-uniformly.

  X: The organic film pattern completely dissolves including the altered layer.

  In addition, when “O: organic film pattern is almost unchanged”, portions other than the altered layer in the organic film pattern 4 are not removed, and an inhibition layer (eg, altered layer or deposited layer caused by Cr etching) is not removed. Only indicates that it has been removed. Since the deteriorated layer by Cr etching is very thin, there is almost no change in the microscopic image. However, even if a portion other than the altered layer in the organic film pattern 4 and the altered layer by Cr etching cannot be removed by the removal process, no change appears in the microscopic image.

  Next, development of the substrate 1 (each substrate 1 in which the column after the chemical treatment is ◯) in which the organic film pattern has hardly changed before and after the above-described removal treatment is made of a 2.38% tetramethylammonium hydroxide aqueous solution. It was re-developed by immersing in the solution at room temperature for 60 seconds.

Next, the substrate 1 was washed with pure water, and pure water was blown off by an air gun that blows out N ₂ gas, followed by natural drying.

  The remaining condition of the organic film pattern 4 on the substrate 1 was observed with an optical microscope, and the change of the organic film pattern 4 was examined.

  The result is shown in the column “After developing solution processing” in FIG. Judgment criteria are as follows.

  ○: The organic film pattern is uniformly dissolved.

  X: The organic film pattern is dissolved non-uniformly.

  -: Developer processing is not performed.

  By performing Cr etching, an altered layer is formed on the surface of the organic film pattern 4. When the organic film pattern 4 is completely removed by the removal treatment using the chemical solution having the composition shown in FIG. 6, the chemical solution has the ability to remove the altered layer by Cr etching, but the removal capability is too strong and the organic The part other than the deteriorated layer in the film pattern 4 is removed. For this reason, the organic film pattern 4 which is the original purpose cannot be reprocessed, which is inappropriate.

  By the removal treatment using the chemical solution having the composition shown in FIG. 6, the portion other than the altered layer in the organic film pattern 4 is removed, but when the altered layer remains due to Cr etching, the chemical solution penetrates from the weak portion of the altered layer, It is considered that portions other than the altered layer in the organic film pattern 4 were dissolved. This case is also inappropriate because the organic film pattern 4 cannot be reprocessed.

  When the organic film pattern is nonuniformly dissolved only partially by the removal treatment using the chemical solution having the composition shown in FIG. 6, the chemical solution does not have the ability to remove the altered layer, but the altered layer caused by Cr etching. It is thought that only the portion other than the altered layer in the organic film pattern 4 was dissolved in the portion from the weak portion of the organic film. Also in this case, since the deteriorated layer remains, the main processing for reworking the organic film pattern 4 cannot be performed, which is inappropriate.

  When the organic film pattern 4 is not substantially changed by the removal treatment using the chemical solution having the composition shown in FIG. 6, this indicates that only the deteriorated layer by Cr etching is removed without removing the organic film pattern 4. Since the deteriorated layer by Cr etching is very thin, almost no change appears in the microscopic image. However, even if the portion other than the altered layer in the organic film pattern 4 and the altered layer by Cr etching cannot be removed by the chemical treatment, no change appears in the microscopic image.

  Therefore, whether or not the deteriorated layer due to Cr etching has been removed is determined by developer processing. The developer cannot remove the deteriorated layer by Cr etching. Therefore, when the developing solution treatment is performed on the organic film pattern 4 in which the deteriorated layer by Cr etching exists, the organic film pattern is non-uniformly dissolved only partially. On the other hand, when the developing solution treatment is performed on the organic film pattern 4 in which no deteriorated layer exists, the organic film pattern is uniform because there is no deteriorated layer by Cr etching that inhibits the developer from penetrating into the organic film pattern. Dissolve.

  From FIG. 6, it is understood that when the chemical solutions according to Examples 1 to 8 are used for the removal process, only the inhibition layer can be removed without removing portions other than the altered layer in the organic film pattern 4.

  In contrast, 2.38% (rounded to 2.4 in FIG. 6) tetramethylammonium hydroxide aqueous solution (Comparative Example 1), 5% hydroxylamine aqueous solution (Comparative Example 3), monoethanolamine and organic Chemical solution consisting of solvent (diethylene glycol and monobutyl ether) (Comparative Example 5), chemical solution consisting only of organic solvent (Comparative Example 6), aqueous solution containing hydroxylamine and monoethanolamine (Comparative Example 7), hydroxylamine concentration is appropriate However, it can be seen that the chemical solution (Comparative Example 9) in which the concentration of the tetramethylammonium hydroxide aqueous solution is insufficient is insufficient in the ability to remove the deteriorated layer. On the other hand, 20% tetramethylammonium hydroxide aqueous solution (Comparative Example 2), chemical solution containing monoethanolamine, organic solvent and water (Comparative Example 4), hydroxylamine concentration is appropriate, but tetramethylammonium hydroxide aqueous solution concentration is Excess liquid (Comparative Example 8), tetramethylammonium hydroxide aqueous solution concentration is appropriate but hydroxylamine concentration is excessive (Comparative Example 10), tetramethylammonium hydroxide aqueous solution concentration is appropriate but hydroxylamine The liquid having the insufficient concentration (Comparative Example 11) is not suitable because the deteriorated layer can be removed, but the organic film pattern that is not deteriorated is completely removed.

  Accordingly, the content of the first component (consisting of at least one of a hydroxylamine derivative and a hydrazine derivative) in the chemical solution according to the above embodiment is 0.5% by weight to 30% by weight. Is preferred. In addition, the content of the developing functional liquid component in the chemical solution according to the above embodiment is preferably 0.2 wt% to 10 wt% (more preferably 0.5 wt% to 10 wt%).

  Next, FIG. 5 will be described.

  FIG. 5 shows the inhibition layer in the original organic film pattern 4 when the mixing ratio of the hydroxylamine derivative and the developing functional liquid component (for example, tetraalkylammonium hydroxide) in the chemical used in the removal treatment is changed. 6 is a graph showing how the removal rate (removal rate: Å / min) and the removal rate (removal rate: Å / min) of portions other than the altered layer in the original organic film pattern 4 change.

  As shown in FIG. 5, the removal rate of the inhibition layer increases as the mixing ratio of the hydroxylamine derivative increases (as the mixing ratio of the tetraalkylammonium hydroxide decreases).

  Further, the removal rate of portions other than the altered layer in the organic film pattern 4 is high when the mixing ratio of the hydroxylamine derivative is 0 (the mixing ratio of tetraalkylammonium hydroxide is 1), and the mixing ratio of the hydroxylamine derivative is 0. As it increases to -0.3 (as the mixing ratio of tetraalkylammonium hydroxide decreases to 1-0.7), the mixing ratio of hydroxylamine derivatives is between 0.3-0.7 ( When the mixing ratio of tetraalkylammonium hydroxide is between 0.7 and 0.3, it is small (almost not removed), and as the mixing ratio of hydroxylamine derivatives increases to 0.7 to 1 (tetraalkyl hydroxide). It increases again (as the ammonium mixing ratio drops from 0.3 to 0).

  For this reason, in order not to remove portions other than the altered layer in the organic film pattern 4, the mixing ratio of the hydroxylamine derivative and the tetraalkylammonium hydroxide in the chemical used in the removal treatment is about 0.3 to The range of 0.7 is preferable, and within this range, it can be said that the higher the removal rate of the inhibition layer, that is, the higher the mixing ratio of the hydroxylamine derivative, the shorter the removal treatment time.

  However, if the implementation time of the removal process is appropriately adjusted, the removal process is preferably performed even if the removal rate of the inhibition layer is smaller than the removal rate of the portion other than the altered layer in the organic film pattern 4. It is feasible.

  For this reason, if ratio V1 / V2 of the speed V1 which dissolves the inhibition layer (altered layer) in the organic film pattern 4 and the speed V2 which dissolves parts other than the altered layer in the organic film pattern 4 is 0.5 or more That is, in the example of FIG. 5, for example, if the mixing ratio of the hydroxylamine derivative and the tetraalkylammonium hydroxide in the chemical used in the removal process is about 0.23 or more, the removal process can be suitably executed. is there.

  However, the slower the speed of dissolving the portion other than the altered layer in the organic film pattern 4, the easier it is to adjust the execution time of the removal process. For this reason, the speed | rate which melt | dissolves parts other than the inhibition layer (altered layer) in the organic film pattern 4 is, for example, preferably 1000 以下 / min or less, more preferably 100 Å / min or less, and 50 以下 / min or less. It is more preferable that

  Here, as the above fourth embodiment, 1) In the case where the following dissolution deformation process is performed following the main process for reworking the organic film pattern 4, 2) the inhibition formed on the surface of the organic film pattern 4 When the following dissolution deformation process is additionally performed after the layer removal process and before the main process for reworking the organic film pattern 4, 3) inhibition formed on the surface of the organic film pattern 4 A dissolution deformation process may be performed before the layer removal process.

  A specific example relating to the dissolution deformation process in the fourth embodiment will be described below.

  In the dissolution deformation process of the organic film pattern, the organic film pattern is dissolved and reflowed by bringing an organic solvent into contact with the organic film pattern (particularly, positive type, resist pattern) (mainly by exposure to an organic solvent gas atmosphere). .

  The dissolution deformation process is performed by, for example, immersing the substrate 1 in an organic solution, so that the organic film pattern 4 formed on the substrate 1 penetrates the organic solution (mainly an organic solvent) and deforms (mainly dissolution reflow deformation). To do.

Alternatively, the dissolution deformation process is performed by, for example, a gas atmosphere process in which an organic solution (mainly an organic solvent) is gasified by bubbling using an inert gas (for example, N ₂ bubbling) and the substrate is exposed to the atmosphere.

  As a pre-treatment, when performing a dissolution / deformation process that dissolves and deforms the organic film pattern formed on the substrate, at least a part of the removal process for removing the inhibition layer on the surface of the organic film pattern is a chemical process that is a wet process. As a result, the inhibition layer can be removed without damaging the substrate and the organic film pattern, and a uniform process can be realized in the subsequent dissolution deformation process.

  Specifically, for example, the deformation process is performed on the substrate by expanding the area of the organic film pattern, integrating the adjacent organic film patterns with each other, flattening the organic film pattern, or the like. It may be performed for the purpose of deforming the organic film pattern so as to be an insulating film covering the circuit pattern.

  Before the dissolution deformation process (organic film pattern processing process), at least one of an exposure process, a development process, a wet etching process, and a dry etching process is appropriately performed on the organic film pattern 4. Anyway.

  In the gas atmosphere treatment, various gases (mainly generated by vaporizing an organic solvent as a raw material) are exposed to the substrate to dissolve and deform the organic film pattern on the substrate (dissolution deformation treatment). That is, the gas atmosphere treatment is performed, for example, in an organic solvent gas atmosphere.

Here, organic solvents suitable for gas atmosphere treatment are divided into an organic solvent as a superordinate concept and an organic solvent as a subordinate concept that embodies it, and are shown below. R represents an alkyl group or a substituted alkyl group, and Ar represents a phenyl group or an aromatic ring other than a phenyl group.
Organic solvent as a superordinate concept:
・ Alcohols (R-OH)
・ Alkoxy alcohols ・ Ethers (R—O—R, Ar—O—R, Ar—O—Ar)
・ Organic solvents of esters, ketones, glycols, alkylene glycols, glycol ethers subordinate concept:
CH ₃ OH, C ₂ H ₅ OH, CH ₃ (CH ₂ ) XOH
・ Isopropyl alcohol (IPA)
・ Ethoxyethanol ・ Methoxy alcohol ・ Long chain alkyl ester ・ Monoethanolamine (MEA)
・ Monoethylamine ・ Diethylamine ・ Triethylamine ・ Monoisopyramine ・ Diisopyramine ・ Triisopyramine ・ Monobutylamine ・ Dibutylamine ・ Tributylamine ・ Hydroxylamine ・ Diethylhydroxylamine ・ Anhydrous diethylhydroxylamine ・ Pyridine ・ Picoline ・ Acetone ・ Acetylacetone ・ Dioxane・ Ethyl acetate ・ Butyl acetate ・ Toluene ・ Methyl ethyl ketone (MEK)
・ Diethyl ketone dimethyl sulfoxide (DMSO)
・ Methyl isobutyl ketone (MIBK)
・ Butyl carbitol ・ n-butyl acetate (nBA)
・ Gamma-butyrolactone ・ Ethyl cellosolve acetate (ECA)
・ Ethyl lactate ・ Ethyl pyruvate ・ 2-heptanone (MAK)
・ 3-methoxybutyl acetate ・ ethylene glycol ・ propylene glycol ・ butylene glycol ・ ethylene glycol monoethyl ether ・ diethylene glycol monoethyl ether ・ ethylene glycol monoethyl ether acetate ・ ethylene glycol monomethyl ether ・ ethylene glycol monomethyl ether acetate ・ ethylene glycol mono-n -Butyl ether, polyethylene glycol, polyprolene glycol, polybutylene glycol, polyethylene glycol monoethyl ether, polydiethylene glycol monoethyl ether, polyethylene glycol monoethyl ether acetate, polyethylene glycol monomethyl ether, polyethylene glycol monomethyl ether acetate, polyethylene Recall mono -n- butyl-methyl-3-methoxypropionate (MMP)
・ Propylene glycol monomethyl ether (PGME)
・ Propylene glycol monomethyl ether acetate (PGMEA)
・ Propylene glycol monopropyl ether (PGP)
・ Propylene glycol monoethyl ether (PGEE)
・ Ethyl-3-ethoxypropionate (FEP)
-Dipropylene glycol monoethyl ether-Tripropylene glycol monoethyl ether-Polypropylene glycol monoethyl ether-Propylene glycol monomethyl ether propionate-Methyl 3-methoxypropionate-Ethyl 3-ethoxypropionate-N-methyl-2-pyrrolidone (NMP)
The gas atmosphere treatment is performed using a gas generated using an organic solvent as a raw material when the organic film pattern is dissolved by the permeation of the organic solvent. For example, when the organic film pattern is water-soluble, acid-soluble, or alkali-soluble, gas atmosphere treatment may be performed using a gas generated using an aqueous solution, an acid solution, or an alkali solution as a raw material.

  In the above, the example using the chemical solution according to the present invention has been described before the removal of the entire organic film or in the case of removing the entire organic film. The above chemical solution can also be used for cleaning the surface or for removing residues after removing the entire organic film.

  Furthermore, the chemical solution according to the present invention can also be used for removing or cleaning residues on the substrate surface at any stage of the above substrate processing method.

  The above-mentioned substrate processing method and chemical solution, the substrate surface cleaning method, and the cleaning method for removing residues after removing the entire organic film are all liquid crystal display (LCD) display devices, that is, vertical electric field type liquid crystal displays. In addition to display devices (LCD) display devices, horizontal electric field type liquid crystal display devices (LCD) display devices, reflective liquid crystal display devices (LCD) display devices, transflective liquid crystal display devices (LCD) display devices, EL display devices, etc. Display devices or semiconductor devices such as flat display panel liquid crystal display devices (LCD), electroluminescence display devices (EL), field emission displays (FED), fluorescent display devices, plasma display panel (PDP) active elements, etc. This method can be applied to the manufacturing method described above, or the manufacturing of a substrate provided with the integrated circuit.

It is a series of process diagrams showing a substrate processing method according to the first embodiment. It is a series of process diagrams showing a substrate processing method according to a second embodiment. It is a series of process diagrams showing a substrate processing method according to a third embodiment. It is a series of process diagrams showing a substrate processing method according to a fourth embodiment. When the mixing ratio of the hydroxylamine derivative and the developer functional component (for example, tetraalkylammonium hydroxide) in the chemical used in the removal process is changed, the removal rate and alteration of the inhibition layer in the original organic film pattern are changed. It is a graph which shows how the removal rate of parts other than a layer changes. It is a figure which shows the Example of a composition of the chemical | medical solution used for a removal process. It is a series of process diagrams showing a conventional substrate processing method.

Explanation of symbols

1 Substrate 2 Conductive film (underlying film)
4 Organic film pattern 5 Organic film pattern 6 Semiconductor film (underlying film)
7 Organic film pattern

Claims (26)

An organic film pattern is formed on the substrate, and an alteration layer formed by altering a surface layer portion of the organic film pattern is formed on the surface of the organic film pattern, and a deposit is deposited on the surface of the organic film pattern. A substrate processing method for performing, in this order, a removal process for removing at least the inhibition layer and a main process for processing the organic film pattern when an inhibition layer comprising at least one of the deposited layer and the inhibition layer is formed. In
The removal process, contains 0.5% to 30% by weight of the first component comprising either at a minimum of hydroxylamine derivatives and hydrazine derivatives, and the developing functional liquid component 0.2% to 10% The substrate processing method characterized by performing using the aqueous solution containing . The substrate processing method according to claim 1 , wherein in the main process, at least a part of the organic film pattern is reduced or at least a part of the organic film pattern is removed. The substrate processing method according to claim 1 , wherein in the main process, all of the organic film pattern is reduced or all of the organic film pattern is removed. The present process, stripping solution, or the substrate processing method according to any one of claims 1 to 3, characterized in that by using a chemical solution having a developing function. A first base film processing step of patterning the base film of the organic film pattern by etching using the organic film pattern as a mask before the removing treatment;
Using the organic film pattern after the first base film processing step or the organic film pattern processed by the main processing as a mask, a second base film processing step for patterning the base film again;
The substrate processing method according to claim 1, further comprising : 6. The substrate processing method according to claim 5 , wherein the pattern of the base film is processed into a taper shape or a step shape by the second base film processing. An organic film pattern processing process for processing the organic film pattern is further provided after at least one of the removal process and the main process,
The organic layer patterning process, the substrate processing method according to any one of claims 1 to 6, characterized in that the dissolving modified process for deforming dissolving said organic film pattern. An organic film pattern processing process for processing the organic film pattern is further provided after at least one of the removal process and the main process,
In the organic film pattern processing,
A heat treatment for heating the organic film pattern;
A dissolution deformation process for dissolving and deforming the organic film pattern;
The substrate processing method according to any one of claims 1 to 6, characterized in that it is carried out in this order. The organic film pattern is subjected to at least one of an exposure process, a development process, a wet etching process, and a dry etching process before the organic film pattern processing process. 9. The substrate processing method according to 7 or 8 . 10. The substrate according to claim 7, further comprising a base film processing step of patterning a base film of the organic film pattern using the organic film pattern before the deformation by the dissolution deformation process as a mask. Processing method. The substrate according to any one of claims 7 to 10 , further comprising a base film processing step of patterning a base film of the organic film pattern using the organic film pattern after the deformation by the dissolution deformation process as a mask. Processing method. The substrate processing method according to claim 7 , wherein the dissolution deformation process is a process of expanding an area of the organic film pattern. The substrate processing method according to claim 7 , wherein the dissolution deformation process is a process of mutually integrating adjacent organic film patterns. The substrate processing method according to claim 7 , wherein the dissolution deformation process is a process of flattening the organic film pattern. The dissolution modification process according to any one of claims 7 to 14, characterized in that a process for the deforming the organic film pattern such that the insulating film covering the circuit pattern formed on a substrate Substrate processing method. 16. The substrate processing method according to claim 7 , wherein the dissolution deformation process is a process of dissolving and reflowing the organic film pattern using an organic solution. The substrate processing method according to claim 16 , wherein the organic solution is a solution containing at least one of organic solvents shown in the following (1) to (5).
(1) Alcohols (R-OH)
(2) Ethers (R—O—R, Ar—O—R, Ar—O—Ar)
(3) Esters (4) Ketones (5) Glycol ethers (However, in (1) and (2), R represents an alkyl group or a substituted alkyl group, and Ar represents a phenyl group or an aromatic ring other than a phenyl group. ) In the removal process, a substrate processing method according to any one of claims 1 to 17, wherein the selectively removing the inhibition layer. In the removal process, removing the inhibition layer, the substrate processing method according to any one of claims 1 to 18, characterized in that exposing and remaining portions other than the affected layer in the organic film pattern. The affected layer, any one of claims 1 to 19, wherein the surface portion of the organic film pattern is one that was altered by at least one of factors of the neglected deterioration, thermal oxidation and thermal curing time The substrate processing method according to one item. The affected layer, the substrate processing method according to any one of claims 1 to 19 surface layer portion of the organic film pattern is characterized in that is obtained by altered by wet etching solution process. The affected layer, the substrate processing method according to any one of claims 1 to 19 surface layer portion of the organic film pattern is characterized in that is obtained by altered by dry etching or ashing. The substrate processing method according to any one of claims 1 to 19 , wherein the deteriorated layer is one in which a surface layer portion of the organic film pattern has changed due to deposition by dry etching. The deposited layer, the substrate processing method according to any one of claims 1 to 23, characterized in that the wherein those formed by dry-etching on the surface of the organic film pattern. Before the removal process, a substrate processing method according to claim 1 to 24, characterized in that it comprises a base film processing step of patterning an underlying film of organic layer pattern by etching using a mask the organic layer pattern . 26. A method for manufacturing a device having a substrate, wherein a display device having a substrate or a semiconductor device having a substrate is manufactured using the substrate processing method according to claim 1 .

Images