CN103165533A - Process method for preventing defects of photoresist during wet etching - Google Patents
Process method for preventing defects of photoresist during wet etching Download PDFInfo
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- CN103165533A CN103165533A CN2013100851841A CN201310085184A CN103165533A CN 103165533 A CN103165533 A CN 103165533A CN 2013100851841 A CN2013100851841 A CN 2013100851841A CN 201310085184 A CN201310085184 A CN 201310085184A CN 103165533 A CN103165533 A CN 103165533A
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Abstract
The invention discloses a process method for preventing defects of photoresist during wet etching. The method comprises the following steps: coating the photoresist on a silicon slice on which a shallow insulation trench is formed and a silicon oxide film is deposited; exposing and developing the photoresist to expose a first silicon oxide area of the silicon oxide film, which is to be subjected to wet etching, and a second silicon oxide area of the silicon oxide film, which is protected by the photoresist; coating a thiocyanate compound-containing crosslinking material solution on a photoresist graph in the same developing machine table which performs development, and heating to ensure that thiocyanate compounds and the surface of the photoresist react to form a polymer crosslinking protection film so as to cure the photoresist graph, and then remove the residual thiocyanate compound-containing crosslinking material solution; performing wet etching to partially remove the silicon oxide film on the first silicon oxide area; and removing the residual photoresist and depositing the silicon oxide film again, so that silicon oxide film dual gate oxides with different thickness can be formed in the first silicon oxide area and the second silicon oxide area.
Description
Technical field
The present invention relates to field of semiconductor manufacture, more particularly, the present invention relates to a kind ofly prevent that photoresist from producing the process of defective in wet etching.
Background technology
Advanced integrated circuit (IC) chip usually can integrated several functions device.The several functions device generally needs corresponding different field-effect transistors (FETs).Multiple-grid oxygen (multiple gate oxide) technique is to make the common method of different field-effect transistors in same chip.There is several different methods can realize multiple-grid oxygen.
For example, Fig. 1-Fig. 5 has showed the fabrication processing of Dual Gate Oxide (dual gate oxide).Form shallow isolated raceway groove 2 and depositing coating photoresist 4 (Fig. 1) on the silicon chip 1 of silicon oxide film 3.Exposure and develop after expose zone 5 that will wet etching and be subject to the zone 6 (Fig. 2) of photoresist 4 protections.The silicon oxide film 3 of wet etching attenuate or removal regional 5 fully (Fig. 3-Fig. 4).Remove after residue photoresist 4 cvd silicon oxide film 3 again, form the silicon oxide film 3 of different-thickness-be so-called Dual Gate Oxide (Fig. 5) in zone 5 and zone 6.Can produce different field-effect transistors on zone 5 and zone 6.
Wet etching silicon oxide film 3 is that the silicon chip 1 that will deposit silicon oxide film 3 is placed in acid solution.Acid solution commonly used is such as hydrofluoric acid (HF).Acid solution also can to photoresist 4 generation effects, form defective when etching oxidation silicon thin film 3.Main defective comprises the residual and carborundum (SiC) of photoresist deposition.The mechanism that forms the photoresist residual defects is acid solution etch photoresist film, and the part macromolecular compound in photoresist film is peeled off out from photoresist film, forms defective at silicon chip surface.The formation mechanism of carborundum deposition defective is that hydrofluoric acid and silica reaction generate hexafluoro SiClx (SiF6), and the macromolecular compound in hexafluoro SiClx and photoresist film further reacts the generation silicon-carbide particles, then forms deposition on silicon chip.
Existingly prevent in the wet etching process that the method that produces the photoresist defective comprises: 1) at photolithographic exposure with after developing, photoresist film is is further baked and banked up with earth, form finer and close photoresist film, make the acid solution of wet etching be difficult to immerse from the gap between the photoresist macromolecular compound, generate defective with the effect of photoresist macromolecular compound; 2) at photolithographic exposure with after developing, photoresist film is carried out ultraviolet light (UV) or plasma cured processing, at surperficial the crosslinked of macromolecular compound that form of photoresist.Crosslinked macromolecule surface can improve the acid-resisting solution etch ability of photoresist effectively.US Patent No. 6498106B1 has reported that adopting low-energy plasma to solidify processes the case that prevents from producing in the wet etching process photoresist defective.
The problem that the existing method that prevents from the wet etching process producing the photoresist defective still exists some to solve.In method 1) in, baking and banking up with earth temperature should not be too high, and the time of baking and banking up with earth is unsuitable oversize.Otherwise can cause the photoetching offset plate figure distortion, and can have a negative impact to production throughput (throughput).Due to the restriction that is subject to baking and banking up with earth temperature He bake and bank up with earth the time, the compactness of baking and banking up with earth rear photoresist film may can't satisfy the requirement of acid-resisting solution etch.Method 2) need to add ultraviolet light (UV) or plasma cured technique after photoetching process.Ultraviolet light (UV) or plasma cured technique need to realize on other board, have not only increased equipment cost, and have extended the production time, have reduced the production throughput.
Summary of the invention
Technical problem to be solved by this invention is for having defects in prior art, a kind of requirement that can satisfy the etch of acid-resisting solution is provided, can guaranteeing that also the photoresist that prevents of production throughput produces the process of defective in wet etching.
In order to realize above-mentioned technical purpose, according to a first aspect of the invention, provide a kind of and prevented that photoresist from producing the process of defective in wet etching, it comprises: be coated with photoresist forming shallow isolated raceway groove and deposited on the silicon chip of silicon oxide film; Complete exposure and development to photoresist, with expose silicon oxide film will wet etching the first region of silicon oxide and be subject to the second region of silicon oxide of photoresist protection; After exposure and developing, in carrying out the same developing machine platform that develops, the cross-linked material solution of coating thiocyanate compounds on photoetching offset plate figure, and heating makes rhodanate compounds and photoresist surface reaction form the crosslinked diaphragm of macromolecule, thereby the curing photoetching offset plate figure is removed the cross-linked material solution of unnecessary thiocyanate compounds subsequently; Carry out wet etching partly to remove the silicon oxide film on the first region of silicon oxide; Remove after the residue photoresist cvd silicon oxide film again, thereby form the silicon oxide film Dual Gate Oxide of different-thickness in the first region of silicon oxide and the second region of silicon oxide.
According to a second aspect of the invention, provide a kind of and prevented that photoresist from producing the process of defective in wet etching, it comprises: be coated with photoresist forming shallow isolated raceway groove and deposited on the silicon chip of silicon oxide film; Complete exposure and development to photoresist, with expose silicon oxide film will wet etching the first region of silicon oxide and be subject to the second region of silicon oxide of photoresist protection; In same developing machine platform, the cross-linked material solution of coating thiocyanate compounds (Thiocyanate) on photoetching offset plate figure, heating makes rhodanate compounds and photoresist surface reaction form the crosslinked diaphragm of macromolecule, thereby the curing photoetching offset plate figure is removed the cross-linked material solution of unnecessary thiocyanate compounds subsequently; Carry out wet etching to remove the silicon oxide film on the first region of silicon oxide fully; Remove after the residue photoresist cvd silicon oxide film again, thereby form the silicon oxide film Dual Gate Oxide of different-thickness in the first region of silicon oxide and the second region of silicon oxide.
Preferably, the step of removing the cross-linked material solution of unnecessary thiocyanate compounds comprises: first process the cross-linked material solution of unnecessary thiocyanate compounds with acid solution, then remove the cross-linked material solution of unnecessary thiocyanate compounds with deionized water.Preferably, acid compound in acid solution is selected from polyacrylic acid, polyisobutene acid, polyvinylsulfonic acid, alkyl carboxylic acid, aryl carboxylic acid, alkyl sulfonic acid, aryl sulfonic acid, the concentration range of acid compound in acid solution is 0.5wt% to 20wt%, preferably 1wt% to 10wt%.
Preferably, the cross-linked material solution of thiocyanate compounds also comprises crosslinking catalyst and/or surfactant in being.
Preferably, crosslinking catalyst is the non-nucleophilic form tertiary amine that is dissolved in organic solvent; The concentration range of non-nucleophilic form tertiary amine is 0.1wt% to 20wt%; Preferably, 0.5% to 5wt%.
Preferably, surfactant is the nonionic surface active agent that is dissolved in organic solvent; The concentration range of surfactant is 50ppm to 10000ppm; Preferably, 100ppm to 1000ppm.
Preferably, in the cross-linked material solution of thiocyanate compounds, the concentration range of rhodanate compounds is 0.1wt% to 100wt%; Preferably, 0.5% to 10wt%.
Preferably, the scope of curing heating-up temperature is 30 ℃ to 180 ℃; Preferably, 50 ℃ to 120 ℃.
Preferably, solidifying the scope of heating time is 15 seconds to 300 seconds; Preferably, 30 seconds to 120 seconds.
Preferably, select photoresist for I Lithography technique, 248 nano-photoetching techniques, 193 nano-photoetching techniques, EUV photoetching process.
Description of drawings
By reference to the accompanying drawings, and by with reference to following detailed description, will more easily to the present invention, more complete understanding be arranged and more easily understand its advantage of following and feature, wherein:
Fig. 1 to Fig. 5 schematically shows the fabrication processing according to the Dual Gate Oxide of prior art.
Fig. 2 to Fig. 8 schematically shows according to of the present invention and prevents that photoresist from producing the part steps of the process of defective in wet etching.
Need to prove, accompanying drawing is used for explanation the present invention, and unrestricted the present invention.Note, the accompanying drawing of expression structure may not be to draw in proportion.And in accompanying drawing, identical or similar element indicates identical or similar label.
Embodiment
In order to make content of the present invention more clear and understandable, below in conjunction with specific embodiments and the drawings, content of the present invention is described in detail.
The＜the first embodiment 〉
Comprise according to photoresist produces defective in wet etching the process that prevents of first embodiment of the invention:
Forming shallow isolated raceway groove 2 and depositing coating photoresist 4(Fig. 1 on the silicon chip 1 of silicon oxide film 3).For example, can select the photoresist that is fit to I Lithography technique, 248 nano-photoetching techniques, 193 nano-photoetching techniques, EUV photoetching process.
Complete exposure and development to photoresist 4, with expose silicon oxide film 3 will wet etching the first region of silicon oxide 5 and be subject to second region of silicon oxide 6(Fig. 2 of photoresist 4 protections).
After exposure and developing; in carrying out the same developing machine platform that develops; the cross-linked material solution of coating thiocyanate compounds on photoresist 4 figures; and heating makes rhodanate compounds material and photoresist 4 surface reactions form the crosslinked diaphragm 7 of macromolecule; thereby solidify photoresist 4 figures, remove subsequently the cross-linked material solution of unnecessary thiocyanate compounds.For example, the step of removing the cross-linked material solution of unnecessary thiocyanate compounds comprises: first process the cross-linked material solution of unnecessary thiocyanate compounds with acid solution, then remove the cross-linked material solution (Fig. 6) of unnecessary thiocyanate compounds with deionized water.
Preferably, the main component of the cross-linked material solution of thiocyanate compounds is the rhodanate compounds, and other compositions can include but not limited to crosslinking catalyst and/or surfactant.
Preferably, in the cross-linked material solution of thiocyanate compounds, the concentration range of rhodanate compounds is 0.1wt% to 100wt%; Preferably, 0.5% to 10wt%.
Preferably, the material of crosslinking catalyst selects to be based on the activity of cross-linking reaction requirement.Preferably, crosslinking catalyst is the non-nucleophilic form tertiary amine (Tertiary amine) that is dissolved in organic solvent; Its concentration range is 0.1wt% to 20wt%; Preferably, 0.5% to 5wt%.
Preferably, the material of surfactant selects to be based on dissolubility and the reactivity requirement of cross-linked material solution.Preferably, surfactant is the nonionic surface active agent that is dissolved in organic solvent; Its concentration range is 50ppm to 10000ppm; Preferably, 100ppm to 1000ppm.
Preferably, the acid compound in acid solution can be polyacrylic acid, polyisobutene acid, polyvinylsulfonic acid, alkyl carboxylic acid, aryl carboxylic acid, alkyl sulfonic acid, aryl sulfonic acid, but is not limited to these compounds.The concentration range of acid compound in acid solution is 0.5wt% to 20wt%.Preferably, 1wt% to 10wt%.
And, preferably, solidify heating-up temperature, its scope is 30 ℃ to 180 ℃; Preferably, 50 ℃ to 120 ℃.And preferably, the scope of solidifying heating time is 15 seconds to 300 seconds.Preferably, 30 seconds to 120 seconds.
Carry out wet etching partly to remove the silicon oxide film 3(Fig. 7 on the first region of silicon oxide 5).
Remove after residue photoresist 4 cvd silicon oxide film 3 again, thereby form silicon oxide film 3 Dual Gate Oxide (Fig. 5) of different-thickness in the first region of silicon oxide 5 and the second region of silicon oxide 6.
Can complete subsequent technique subsequently, produce different field-effect transistors on the first region of silicon oxide 5 and the second region of silicon oxide 6.
The＜the second embodiment 〉
Comprise according to photoresist produces defective in wet etching the process that prevents of second embodiment of the invention:
Forming shallow isolated raceway groove 2 and depositing coating photoresist 4(Fig. 1 on the silicon chip 1 of silicon oxide film 3).For example, can select the photoresist that is fit to I Lithography technique, 248 nano-photoetching techniques, 193 nano-photoetching techniques, EUV photoetching process.
Complete exposure and development to photoresist 4, with expose silicon oxide film 3 will wet etching the first region of silicon oxide 5 and be subject to second region of silicon oxide 6(Fig. 2 of photoresist 4 protections).
In same developing machine platform; the cross-linked material solution of coating thiocyanate compounds on photoresist 4 figures; heating makes rhodanate compounds material and photoresist 4 surface reactions form the crosslinked diaphragm 7 of macromolecule; thereby solidify photoresist 4 figures, remove subsequently the cross-linked material solution of unnecessary thiocyanate compounds.For example, the step of removing the cross-linked material solution of unnecessary thiocyanate compounds comprises: first process the cross-linked material solution of unnecessary thiocyanate compounds with acid solution, then remove the cross-linked material solution (Fig. 6) of unnecessary thiocyanate compounds with deionized water.
Preferably, the main component of the cross-linked material solution of thiocyanate compounds is the rhodanate compounds, and other compositions can include but not limited to crosslinking catalyst and/or surfactant.
Preferably, in the cross-linked material solution of thiocyanate compounds, the concentration range of rhodanate compounds is 0.1wt% to 100wt%; Preferably, 0.5% to 10wt%.
Preferably, the material of crosslinking catalyst selects to be based on the activity of cross-linking reaction requirement.Preferably, crosslinking catalyst is the non-nucleophilic form tertiary amine (Tertiary amine) that is dissolved in organic solvent; Its concentration range is 0.1wt% to 20wt%; Preferably, 0.5% to 5wt%.
Preferably, the material of surfactant selects to be based on dissolubility and the reactivity requirement of cross-linked material solution.Preferably, surfactant is the nonionic surface active agent that is dissolved in organic solvent; Its concentration range is 50ppm to 10000ppm; Preferably, 100ppm to 1000ppm.
Preferably, the acid compound in acid solution can be polyacrylic acid, polyisobutene acid, polyvinylsulfonic acid, alkyl carboxylic acid, aryl carboxylic acid, alkyl sulfonic acid, aryl sulfonic acid, but is not limited to these compounds.The concentration range of acid compound in acid solution is 0.5wt% to 20wt%.Preferably, 1wt% to 10wt%.
And, preferably, solidify heating-up temperature, its scope is 30 ℃ to 180 ℃; Preferably, 50 ℃ to 120 ℃.And preferably, the scope of solidifying heating time is 15 seconds to 300 seconds.Preferably, 30 seconds to 120 seconds.
Carry out wet etching to remove the silicon oxide film 3(Fig. 8 on the first region of silicon oxide 5 fully).
Remove after residue photoresist 4 cvd silicon oxide film 3 again, thereby form silicon oxide film 3 Dual Gate Oxide (Fig. 5) of different-thickness in the first region of silicon oxide 5 and the second region of silicon oxide 6.
Can complete subsequent technique subsequently, produce different field-effect transistors on the first region of silicon oxide 5 and the second region of silicon oxide 6.
According to above-described embodiment, can effectively improve the compactness on photoresist 4 top layers, improve photoresist 4 acid-resisting solution etch abilities, reduce photoresist 4 and produce the probability of defective in the wet etching process, and do not need extra board, reduced processing step and cost of manufacture, improved production capacity.
Thus; the present invention is directed to the problems of the prior art; proposed to adopt the rhodanate compounds in developing machine platform, post-develop to be carved the method for glue pattern chemosetting processing at the photoresist 4 crosslinked diaphragms 7 of surface formation macromolecule; the requirement of acid-resisting solution etch can be satisfied, also the production throughput can be guaranteed.
In addition, need to prove, unless stated otherwise or point out, otherwise the term in specification " first ", " second ", " the 3rd " etc. describe each assembly of only being used for distinguishing specification, element, step etc., rather than are used for logical relation between each assembly of expression, element, step or ordinal relation etc.
Be understandable that, although the present invention with the preferred embodiment disclosure as above, yet above-described embodiment is not to limit the present invention.For any those of ordinary skill in the art, do not breaking away from technical solution of the present invention scope situation, all can utilize the technology contents of above-mentioned announcement to make many possible changes and modification to technical solution of the present invention, or be revised as the equivalent embodiment of equivalent variations.Therefore, every content that does not break away from technical solution of the present invention, all still belongs in the scope of technical solution of the present invention protection any simple modification made for any of the above embodiments, equivalent variations and modification according to technical spirit of the present invention.
Claims (10)
1. one kind prevents that photoresist from producing the process of defective in wet etching, is characterized in that comprising:
Be coated with photoresist forming shallow isolated raceway groove and deposited on the silicon chip of silicon oxide film;
Complete exposure and development to photoresist, with expose silicon oxide film will wet etching the first region of silicon oxide and be subject to the second region of silicon oxide of photoresist protection;
After exposure and developing, in carrying out the same developing machine platform that develops, the cross-linked material solution of coating thiocyanate compounds on photoetching offset plate figure, and heating makes rhodanate compounds and photoresist surface reaction form the crosslinked diaphragm of macromolecule, thereby the curing photoetching offset plate figure is removed the cross-linked material solution of unnecessary thiocyanate compounds subsequently;
Carry out wet etching partly to remove the silicon oxide film on the first region of silicon oxide;
Remove after the residue photoresist cvd silicon oxide film again, thereby form the silicon oxide film Dual Gate Oxide of different-thickness in the first region of silicon oxide and the second region of silicon oxide.
2. one kind prevents that photoresist from producing the process of defective in wet etching, is characterized in that comprising:
Be coated with photoresist forming shallow isolated raceway groove and deposited on the silicon chip of silicon oxide film;
Complete exposure and development to photoresist, with expose silicon oxide film will wet etching the first region of silicon oxide and be subject to the second region of silicon oxide of photoresist protection;
In same developing machine platform, the cross-linked material solution of coating thiocyanate compounds on photoetching offset plate figure, heating makes rhodanate compounds and photoresist surface reaction form the crosslinked diaphragm of macromolecule, thereby the curing photoetching offset plate figure is removed the cross-linked material solution of unnecessary thiocyanate compounds subsequently;
Carry out wet etching to remove the silicon oxide film on the first region of silicon oxide fully;
Remove after the residue photoresist cvd silicon oxide film again, thereby form the silicon oxide film Dual Gate Oxide of different-thickness in the first region of silicon oxide and the second region of silicon oxide.
3. according to claim 1 and 2ly prevent that photoresist from producing the process of defective in wet etching, it is characterized in that, the step of removing the cross-linked material solution of unnecessary thiocyanate compounds comprises: first process the cross-linked material solution of unnecessary thiocyanate compounds with acid solution, then remove the cross-linked material solution of unnecessary thiocyanate compounds with deionized water.
4. according to claim 1 and 2ly prevent that photoresist from producing the process of defective in wet etching, it is characterized in that, also comprise crosslinking catalyst and/or surfactant in the cross-linked material solution of thiocyanate compounds.
5. according to claim 1 and 2ly prevent that photoresist from producing the process of defective in wet etching, it is characterized in that, in the cross-linked material solution of thiocyanate compounds, the concentration range of rhodanate compounds is 0.1wt% to 100wt%; Preferably, 0.5% to 10wt%.。
6. according to claim 4ly prevent that photoresist from producing the process of defective in wet etching, it is characterized in that, crosslinking catalyst is the non-nucleophilic form tertiary amine that is dissolved in organic solvent; The concentration range of non-nucleophilic form tertiary amine is 0.1wt% to 20wt%; Preferably, 0.5% to 5wt%.
7. according to claim 4ly prevent that photoresist from producing the process of defective in wet etching, it is characterized in that, surfactant is the nonionic surface active agent that is dissolved in organic solvent; The concentration range of surfactant is 50ppm to 10000ppm; Preferably, 100ppm to 1000ppm.
8. according to claim 6 or 7 describedly prevent that photoresist from producing the process of defective in wet etching, it is characterized in that, the scope of solidifying heating-up temperature is 30 ℃ to 180 ℃; Preferably, 50 ℃ to 120 ℃.
9. according to claim 6 or 7 describedly prevent that photoresist from producing the process of defective in wet etching, it is characterized in that, the scope of solidifying heating time is 15 seconds to 300 seconds; Preferably, 30 seconds to 120 seconds.
10. according to claim 3ly prevent that photoresist from producing the process of defective in wet etching, it is characterized in that, acid compound in acid solution is selected from polyacrylic acid, polyisobutene acid, polyvinylsulfonic acid, alkyl carboxylic acid, aryl carboxylic acid, alkyl sulfonic acid, aryl sulfonic acid, the concentration range of acid compound in acid solution is 0.5wt% to 20wt%, preferably 1wt% to 10wt%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103474339A (en) * | 2013-09-22 | 2013-12-25 | 上海华力微电子有限公司 | Method for manufacturing high-evenness grid electrode lines |
| CN103474337A (en) * | 2013-09-22 | 2013-12-25 | 上海华力微电子有限公司 | Method for manufacturing high-evenness grid electrode lines |
| CN111474833A (en) * | 2020-05-29 | 2020-07-31 | 常州时创新材料有限公司 | Photoetching wetting liquid and application thereof |
| CN115047728A (en) * | 2022-07-01 | 2022-09-13 | 中国科学院光电技术研究所 | Imaging structure protection method and structure for plasma resonant cavity lens photoetching |
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| CN1540723A (en) * | 2003-10-30 | 2004-10-27 | 上海集成电路研发中心有限公司 | Method for preparing dual-gate containing nitrogen in silicon oxide layer of semiconductor device |
| US20080199814A1 (en) * | 2006-12-06 | 2008-08-21 | Fujifilm Electronic Materials, U.S.A., Inc. | Device manufacturing process utilizing a double patterning process |
| CN101796631A (en) * | 2007-09-07 | 2010-08-04 | 飞思卡尔半导体公司 | Dual gate oxide device is integrated |
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- 2013-03-15 CN CN2013100851841A patent/CN103165533A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1540723A (en) * | 2003-10-30 | 2004-10-27 | 上海集成电路研发中心有限公司 | Method for preparing dual-gate containing nitrogen in silicon oxide layer of semiconductor device |
| US20080199814A1 (en) * | 2006-12-06 | 2008-08-21 | Fujifilm Electronic Materials, U.S.A., Inc. | Device manufacturing process utilizing a double patterning process |
| CN101796631A (en) * | 2007-09-07 | 2010-08-04 | 飞思卡尔半导体公司 | Dual gate oxide device is integrated |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103474339A (en) * | 2013-09-22 | 2013-12-25 | 上海华力微电子有限公司 | Method for manufacturing high-evenness grid electrode lines |
| CN103474337A (en) * | 2013-09-22 | 2013-12-25 | 上海华力微电子有限公司 | Method for manufacturing high-evenness grid electrode lines |
| CN111474833A (en) * | 2020-05-29 | 2020-07-31 | 常州时创新材料有限公司 | Photoetching wetting liquid and application thereof |
| CN115047728A (en) * | 2022-07-01 | 2022-09-13 | 中国科学院光电技术研究所 | Imaging structure protection method and structure for plasma resonant cavity lens photoetching |
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Application publication date: 20130619 |