CN1321755C - Method for cleaning silicon surface and method for manufacturing thin film transistors using this method - Google Patents
Method for cleaning silicon surface and method for manufacturing thin film transistors using this method Download PDFInfo
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- CN1321755C CN1321755C CNB031017274A CN03101727A CN1321755C CN 1321755 C CN1321755 C CN 1321755C CN B031017274 A CNB031017274 A CN B031017274A CN 03101727 A CN03101727 A CN 03101727A CN 1321755 C CN1321755 C CN 1321755C
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- 238000000034 method Methods 0.000 title claims abstract description 78
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 71
- 239000010703 silicon Substances 0.000 title claims abstract description 71
- 238000004140 cleaning Methods 0.000 title claims abstract description 62
- 239000010409 thin film Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007800 oxidant agent Substances 0.000 claims abstract description 27
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract 11
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 27
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000004973 liquid crystal related substance Substances 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 2
- 239000010410 layer Substances 0.000 description 47
- 239000013078 crystal Substances 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 23
- 229910021419 crystalline silicon Inorganic materials 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 239000002210 silicon-based material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 4
- 238000005224 laser annealing Methods 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
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- Thin Film Transistor (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
本发明提供一种清洗硅表面的方法，其包括以下步骤。首先，使用氧化剂溶液第一次清洗硅表面。接着，以HF蒸气或液体清洗硅表面，以氢气水或去离子水配合超音波(megasonic)清洗硅表面。最后，使用氧化剂溶液第二次清洗硅表面。本发明的清洗方法可应用于薄膜晶体管(TFT)的制作，所得TFT具有较高的电子迁移率。
The present invention provides a method for cleaning a silicon surface, which comprises the following steps. First, the silicon surface is cleaned for the first time using an oxidant solution. Then, the silicon surface is cleaned with HF vapor or liquid, and the silicon surface is cleaned with hydrogen water or deionized water combined with megasonics. Finally, the silicon surface is cleaned for the second time using an oxidant solution. The cleaning method of the present invention can be applied to the manufacture of thin film transistors (TFTs), and the resulting TFTs have a higher electron mobility.
Description
Technical field
The present invention relates to a kind of method of cleaning silicon face, particularly in the TFT processing procedure of Thin Film Transistor-LCD (TFT-LCD), clean the method for silicon face.
Background technology
Making semiconducter IC and making in thin film transistor (TFT)-LCD array (TFT-LCD array) processing procedure, the cleaning performance of silicon materials has significant effects for the quality of final IC assembly and TFT array.
In semiconducter IC is made, Caros (H
2SO
4/ H
2O
2), SCl (standard clean 1; NH
4OH/H
2O
2), and SC2 (standard clean 2; HCl/H
2O
2) be widely used in the cleaning of Silicon Wafer.Though this mode has better cleaning effect, shortcoming produces environmental issue for needing to use a large amount of chemicals, needs extra disposal cost.In addition, ozone and HF also are used to clean Silicon Wafer.For example, among the U.S.Patent Application Publication No.2001/0017143 A1, use Ozone Water (ozone water) and HF to clean semiconductor silicon wafer.U.S.PatentNo.6 in 240,933, uses the ozone water cleaning semiconductor Silicon Wafer, removes oxide with steam again.U.S.PatentNo.6 mentions for semi-conductive cleaning in 348,157, uses Ozone Water, HF (cooperating the ultrasonic concussion), deionized water, HF and deionized water in regular turn.
In non-crystalline silicon tft-LCD (amorphous silicon TFT-LCD) processing procedure, the cleaning of non-crystalline silicon is to use CJ (cavitation-jet; The air pocket ejection), brush, Ozone Water (ozone water) or ultraviolet and ozone modes such as (UV ozone).CJ or brush clean relatively poor less than the removal efficient of 1 μ m particle for particle diameter, the concentration of Ozone Water if too low (＜10ppm), cleaning performance is also bad, and ultraviolet and ozone has good clearance for organic matter, but then not good for the removal effect of metal pollutant.
Because compound crystal silicon TFT has higher electron mobility, reaction time, higher resolution ratio faster compared with non-crystalline silicon tft, therefore, at present compound crystal silicon TFT widespread usage in LCD to drive LCD.The preparation method of compound crystal silicon TFT generally adopts low temperature compound crystal silicon method for making (LTPS; Low temperature polysilicon), that is, form non-crystalline silicon earlier, utilize laser annealing (laser annealing) that recrystallized amorphous silicon is formed compound crystal silicon again.
Therefore, be necessary to develop and a kind of effective cleaning method, cleaning the Silicon Wafer of semiconducter IC, and the non-crystalline silicon of TFT-LCD or compound crystal silicon
Summary of the invention
In view of this, purpose of the present invention is for a kind of method of cleaning silicon face that provides is provided.Cleaning method of the present invention is suitable for all silicon materials, comprises monocrystalline silicon wafer crystal, non-crystalline silicon, or compound crystal silicon.Cleaning method of the present invention has excellent cleaning effect, and by cleaning method of the present invention, resulting TFT has higher electron mobility.
For finishing purpose of the present invention, the method that the present invention cleans silicon face may further comprise the steps.At first, use oxidizing agent solution to clean silicon face for the first time.Then, clean silicon face, cooperate ultrasonic (megasonic) to clean silicon face with hydrogen water or deionized water with HF steam or liquid.At last, re-use oxidizing agent solution and clean silicon face for the second time.
According to specific embodiments of the invention, cleaning method of the present invention can be used the cleaning of silicon materials in the TFT processing procedure, may further comprise the steps: form amorphous silicon layer as active layers on substrate; Clean for the amorphous silicon layer surface; And formation brake-pole dielectric layer, gate, source electrode and drain electrode.The invention is characterized in that it may further comprise the steps to the cleaning on amorphous silicon layer surface.At first, use oxidizing agent solution to clean this amorphous silicon layer surface for the first time.Then, clean the amorphous silicon layer surface, cooperate ultrasonic to clean the amorphous silicon layer surface with hydrogen water or deionized water with HF steam or liquid.At last, re-use oxidizing agent solution and clean the amorphous silicon layer surface for the second time.
Description of drawings
Fig. 1 shows according in the preferred embodiment of the present invention manufacturing compound crystal silicon TFT processing procedure, for the flow chart of amorphous silicon layer cleaning method.
Fig. 2 a to 2i shows the processing procedure profile according to gate formula (top-gate) compound crystal silicon TFT array in the preferred embodiment of the present invention manufacturing.
Fig. 3 shows and uses the comparison for each metal ion species clearance on the Silicon Wafer of cleaning method of the present invention and conventional clean method.
Fig. 4 a and Fig. 4 b show the Id-Vg figure that uses cleaning method of the present invention and conventional clean method gained NTFT and PTFT respectively.
Symbol description
10～substrate,
12～buffer insulation layer,
20～amorphous silicon layer,
22,24～compound crystal silicon layer,
PR1, PR2, PR3～photoresistance pattern,
32～n type source/drain region,
34～lightly mixed drain area (LDD),
36～p type source/drain region,
40～brake-pole dielectric layer,
42～interlayer dielectric layer,
43～the first openings,
46～purification layer,
47～the second openings,
50～gate layer,
52～source/drain electrode,
60～pixel electrode.
The specific embodiment
The invention provides a kind of method of cleaning silicon face, may further comprise the steps.At first, use oxidizing agent solution to clean silicon face for the first time.Then, clean silicon face, cooperate ultrasonic (megasonic) to clean silicon face with hydrogen water or deionized water with HF steam or liquid.At last, use oxidizing agent solution to clean silicon face for the second time.
Cleaning method of the present invention is applicable to various silicon materials, comprises monocrystalline silicon wafer crystal, non-crystalline silicon, or compound crystal silicon.For example, the present invention is applicable to the cleaning of monocrystalline silicon wafer crystal, non-crystalline silicon and compound crystal silicon in the semiconducter IC processing procedure, the cleaning of non-crystalline silicon or compound crystal silicon in the TFT-LCD processing procedure.
Fig. 1 shows according in the preferred embodiment of the present invention manufacturing compound crystal silicon TFT processing procedure, for the flow chart of amorphous silicon layer cleaning method.Fig. 2 a to 2i shows the processing procedure profile according to gate formula (top-gate) compound crystal silicon TFT in the preferred embodiment of the present invention manufacturing.
At first, a that sees figures.1.and.2 simultaneously carries out step S11, forms buffer insulation layer 12 and amorphous silicon layer 20 on substrate 10 in regular turn.Substrate 10 can be transparency carrier, for example glass or plastics.Buffer insulation layer 12 can be silicon nitride or silica, perhaps, can comprise two-layer: the combination of silicon nitride layer and silicon oxide layer.Amorphous silicon layer can use silicomethane (silane; SiH
4) be reacting gas, with plasma auxiliary chemical vapor deposition method (PECVD; Plasma-enhanced chemical vapor deposition) or the long-pending method (LPCVD in low pressure chemical gas phase Shen; Lowpressure chemical vapor deposition) forms.After amorphous silicon layer 20 forms, carry out dehydrogenationization (dehydration).
Then, carry out cleaning step of the present invention, that is, carry out step S12 to S15.Below narrate cleaning step respectively.At first, carry out step S12, use oxidizing agent solution to clean the amorphous silicon layer surface for the first time.Clean with oxidizing agent solution, can make that the amorphous silicon layer surface is oxidized, and produce natural oxide (native oxide), so, organic pollution and contaminant metal ions can be coated (trap) in oxide.This oxidizing agent solution can be the aqueous solution ozoniferous, or can be hydrogen peroxide.When using the aqueous solution ozoniferous, ozone concentration can be 15 to 30ppm.Can add HCl again in the oxidizing agent solution, concentration can be 15 to 30ppm, makes the efficient of removing metal higher.
Then, carry out step S13, with HF steam or the clear amorphous silicon layer surface of liquid.HF steam or strength of fluid can be 0.5 to 2 weight %.Use HF to clean and to remove the natural oxide on amorphous silicon layer surface, therefore, make the organic pollution and the contaminant metal ions that are coated in the oxide remove thereupon.
Then, carry out step S14, cooperate ultrasonic to clean amorphous silicon layer, particle (particles) shake can be fallen with hydrogen water or deionized water.Above-mentioned hydrogen water or deionized water also can comprise alkaline components, for example ammoniacal liquor (NH
4OH), to increase the removal efficient of particle.
Then, carry out step S15, use oxidizing agent solution to carry out the second time and clean.The prescription of this oxidizing agent solution can be with for the first time to use oxidizing agent solution to clean employed prescription identical or different.For the second time use the purpose of oxidizing agent solution to be, make dangling bonds (dangling bond) passivation (pssivation) of amorphous silicon surfaces.
In the above-mentioned cleaning step S12 to S15 that carries out, employed various cleaning agents comprise oxidizing agent solution, HF liquid, hydrogen water, deionized water etc., all can adopt to be sprayed on the silicon materials or with the mode that silicon materials are immersed in the cleaning agent and carry out.
Then, the b that sees figures.1.and.2 simultaneously carries out step S16, makes amorphous silicon layer 20 carry out crystallization, for example uses excimer laser annealing (ELA; Excimer laser annealing) mode is carried out crystallization, and forms compound crystal silicon layer 22.
At last, carry out step S17, carry out remaining TFT array processing procedure,, obtain compound crystal silicon TFT array at last to finish TFT array processing procedure.
Following with reference to Fig. 2 c to Fig. 2 i, remaining TFT array processing procedure is described.With reference to Fig. 2 c,,, and obtain being divided into the compound crystal silicon layer 24 in I district and II district with compound crystal silicon layer 22 patternings with lithography process and etching method.
Then,, form photoresistance pattern P R1, use photoresistance pattern P R1, carry out heavy doping with phosphorus for compound crystal silicon layer 24, and form n type source/drain region 32 in the I district for the cover curtain with reference to Fig. 2 d.Then,, remove removing photoresistance pattern P R1, form brake-pole dielectric layer 40, form photoresistance pattern P R2 again with reference to Fig. 2 e.Use photoresistance pattern P R2 for the cover curtain, carry out light dope with phosphorus for compound crystal silicon layer 24, and form lightly mixed drain area (LDD in the inboard of I district n type source/drain region 32; Lightly-doped drain) 34.
Then,, remove removing photoresistance pattern P R2, form photoresistance pattern P R3 with reference to Fig. 2 f.Use photoresistance pattern P R3 for the cover curtain, carry out heavy doping with boron for compound crystal silicon layer 24, and form p type source/drain region 36 in the II district.
Then,, remove removing photoresistance pattern P R3, on brake-pole dielectric layer 40, form the metal level (not shown), carry out little shadow and etching for metal level again, and on the correspondence position of compound crystal silicon layer 24, form gate layer 50 with reference to Fig. 2 g.So far, the I district forms NTFT, and the II district forms PTFT.
Then,, form interlayer dielectric layer (interlayer dielectric) 42, in interlayer dielectric layer 42, form first opening 43 that reaches source/ drain region 32 and 36 again with reference to Fig. 2 h.Then, metal is inserted in first opening 43, and formation source/drain electrode 52.
Then,, form passivation layer (passivation layer) 46, in passivation layer 46, form second opening 47 of the drain electrode 52 that reaches NTFT again with reference to 2i.Then, with pixel electrode 60, ITO (indium-tin oxide for example; Tin indium oxide) inserts in second opening 47, so far finish TFT array processing procedure, obtain the TFT array shown in Fig. 2 i.This TFT array can be combined with preceding transparency carrier (as colored filter substrate) and liquid crystal, and constitutes the TFT-LCD panel.
Below test cleaning method of the present invention (uses O
3And HF) and traditionally only use ozone (O
3) cleaning method, for the comparison of various metal removal rates on the Silicon Wafer.Silicon Wafer is immersed in the various metal ion solutions of 20ppm, oven dry makes the concentration of metal ion be about 10
13Atom/cm
2After having the Silicon Wafer of metal ion to carry out cleaning method of the present invention and conventional clean method respectively the surface, survey concentration of metal ions again, obtain the clearance of various metals, the result as shown in Figure 3.As seen from Figure 3, use cleaning method of the present invention, for the clearance of various metals all than using conventional method for good.
The TFT of above-mentioned gained Fig. 2 i comprises NTFT and PTFT.According to similar method, produce NTFT and PTFT with conventional clean method (only cleaning) with HF.Table 1 and table 2 are respectively the electrical data of cleaning method of the present invention and obtained NTFT of conventional clean method and PTFT, and Fig. 4 a and Fig. 4 b then show the Id-Vg figure of cleaning method of the present invention and obtained NTFT of conventional clean method and PTFT respectively.
The electrical data of table 1NTFT
| Conventional clean method (only cleaning) with HF | Cleaning method of the present invention | |
| Vt(V) | 1.8 | 2.5 |
| Ufe(cm 2/V-s) | 65 | 120 |
| SS(mV/decade) | 0.54 | 0.44 |
The electrical data of table 2PTFT
| Conventional clean method (only cleaning) with HF | Cleaning method of the present invention | |
| Vt(V) | -5.5 | -2.27 |
| Ufe(cm 2/V-s) | 55 | 96 |
| SS(mV/decade) | 0.5 | 0.4 |
Vt: critical voltage (threshold voltage)
Ufe: an effect mobility (field effect mobility)
SS: the subcritical amplitude of oscillation (subthreshold swing)
By table 1, table 2, Fig. 4 a and Fig. 4 b as seen, use cleaning method gained TFT of the present invention to have excellent electrical property, and electron mobility is higher.
Though the present invention discloses as above with preferred embodiment; right its is not in order to restriction the present invention; anyly know those skilled in the art; without departing from the spirit and scope of the present invention; change and retouching when doing, thus protection scope of the present invention when with claims of the present invention the person of being defined be as the criterion.
Claims (23)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031017274A CN1321755C (en) | 2003-01-21 | 2003-01-21 | Method for cleaning silicon surface and method for manufacturing thin film transistors using this method |
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|---|---|---|---|
| CNB031017274A CN1321755C (en) | 2003-01-21 | 2003-01-21 | Method for cleaning silicon surface and method for manufacturing thin film transistors using this method |
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| CN1519060A CN1519060A (en) | 2004-08-11 |
| CN1321755C true CN1321755C (en) | 2007-06-20 |
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Cited By (1)
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|---|---|---|---|---|
| CN106862114A (en) * | 2017-02-09 | 2017-06-20 | 同济大学 | A kind of cleaning method before lbo crystal surface coating |
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| WO2007062111A1 (en) * | 2005-11-23 | 2007-05-31 | Fsi International, Inc. | Process for removing material from substrates |
| KR100678482B1 (en) * | 2006-01-17 | 2007-02-02 | 삼성전자주식회사 | Cleaning solution of silicon surface and manufacturing method of semiconductor device using same |
| JP5589968B2 (en) * | 2011-06-17 | 2014-09-17 | 信越半導体株式会社 | Semiconductor wafer cleaning method |
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| CN109742015A (en) * | 2019-01-08 | 2019-05-10 | 京东方科技集团股份有限公司 | Film surface processing method and film surface processing equipment |
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| CN106862114B (en) * | 2017-02-09 | 2018-10-26 | 同济大学 | A kind of cleaning method before lbo crystal surface coating |
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| CN1519060A (en) | 2004-08-11 |
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