CN102709404A - Method for preparing polycrystalline silicon film by carrying out induced crystallization on amorphous silicon film by using metallic copper under low temperature - Google Patents
Method for preparing polycrystalline silicon film by carrying out induced crystallization on amorphous silicon film by using metallic copper under low temperature Download PDFInfo
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- CN102709404A CN102709404A CN2012102057185A CN201210205718A CN102709404A CN 102709404 A CN102709404 A CN 102709404A CN 2012102057185 A CN2012102057185 A CN 2012102057185A CN 201210205718 A CN201210205718 A CN 201210205718A CN 102709404 A CN102709404 A CN 102709404A
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Abstract
The invention relates to a preparation method of a polycrystalline silicon film, in particular to a method for preparing a polycrystalline silicon film by carrying out induced crystallization on an amorphous silicon film by cycle annealing under low temperature by using catalytic action of metallic copper. The main technical scheme of the invention is as follows: the method comprises the following steps of: growing a substrate/amorphous silicon/silicon dioxide/copper film structure on a glass substrate, then carrying out cycle annealing, putting a sample in corrosive liquid for corroding after first annealing is finished, and carrying out cycle annealing and corroding again, and drying the sample with nitrogen; and finally preparing the polycrystalline silicon film prepared by induced crystallization by copper, wherein the grain size is about 50-200nm. The method disclosed by the invention can ease the problem of serious metal pollution in the traditional MIC (Metal Induced Crystallization) technology and is suitable for the field of thin film field effect transistors and thin-film solar cells.
Description
Technical field
The present invention relates to a kind of preparation method of polysilicon membrane, is exactly to utilize the catalytic action of metallic copper to induce the method for amorphous silicon membrane crystallization for polysilicon membrane at low temperatures specifically.
Background technology
The method for preparing at present polysilicon membrane mainly will have: Low Pressure Chemical Vapor Deposition (LPCVD), solid phase crystallization method (SPC), PRK revulsive crystallization method (ELA), rapid thermal annealing crystallization method (RTA) etc.
It is fine and close, even to be equipped with the polysilicon film forming with the LPCVD legal system, and the production of ability large tracts of land, when still preparing in this way; Required substrate temperature is higher, and deposition velocity is slower, can not use cheap glass to be substrate; The particle that polysilicon membrane generated that the most important thing is this method deposit is less; Cause the film crystal boundary many, defective is many, influences the efficient of follow-up solar cell;
Solid phase crystallization method (SPC) is though process equipment is simple; But the selectional restriction to baseplate material is bigger; Be less compliant on the glass substrate and make; Even if on other can resistant to elevated temperatures base material the deposit polysilicon membrane also have temperature required too high, consuming time too high, power consumption is big, the factor restriction that cost is too high;
PRK crystallization method (ELA) at first is the laser beam irradiation amorphous silicon surfaces with different-energy density, makes the amorphous silicon heat fused, and crystallization takes place during liquid amorphous silicon cools.This just requires laser energy density moderate; When laser energy density during less than crystallization threshold energy density amorphous silicon crystallization does not take place; And when too high; Owing to fail to form the solid liquid interface of recrystallization, the liquify area temperature in the film is more much higher than fusing point, and decrystallized or controlled micro crystallization takes place the too fast polysilicon that directly causes of cooling rate.Moreover laser induced crystallization method complex equipments, manufacturing cost is higher, for obviously not being optimal selection in the suitability for industrialized production of striving for economic benefits.
Short annealing method (RTA) processing procedure is used the method intensification cooling of halogen tungsten light heating.So-called " fast " is meant that as its name suggests intensification and cooling rate are very fast, several Baidu of can heating up in several seconds again, so the variation of temperature amount is easy to control in the unit interval.Time, temperature through control temperature rise period, stabilization sub stage and this three phases of cooling stage; The film that can prepare the various grain sizes size, but generally speaking, use the polysilicon grain size of RTA annealing method preparation little; Crystals crystal boundary density is big; Fault in material density is high, and belongs to the high annealing method, and being not suitable for glass is the substrate preparation polysilicon.
Metal-induced crystallization (metal-induced crystallization, MIC) method is the method that a kind of low temperature prepares polysilicon membrane, it mainly is to utilize the catalytic action of metal to reduce the nucleation temperature of amorphous silicon, reaches the purpose of nucleation under the low temperature.Specifically, be exactly in amorphous silicon (a-Si) vapor deposition or sputter layer of metal film above the film, perhaps deposition one deck amorphous silicon membrane on the substrate of metal-plated membrane carries out the technology that annealing in process forms polysilicon membrane with sample then.In the process of annealing, through contacting of amorphous silicon and metal, improved the diffusion rate of metallic atom and Si atom, reduced amorphous silicon crystallization temperature, shortened crystallization time.Metal-induced crystallization (MIC) method not only can use cheap glass as substrate, the most important thing is, can make the polysilicon membrane of big crystal grain, reduces crystal boundary density and defect concentration and good uniformity.
Summary of the invention
Because using MIC aluminium to induce is the problem that a certain amount of metallic pollution is always arranged; And in order to combine in the application facet of TFT and the of new generation technological copper-connection in the semiconductor manufacturing; Utilize the inductivity of copper, the present invention uses the method for the crystallizing amorphous silicon thin film of copper inducible of cycle annealing formula to prepare polysilicon membrane.
In order to reach above-mentioned purpose, the present invention adopts following technical scheme to realize.
(a) cleaning of substrate glass: at first use the surperficial dirt of TritonX solvent clean glass substrate, then this substrate is placed on acetone, absolute ethyl alcohol and deionized water for ultrasonic ripple respectively and cleaned 15 minutes, and dry up with nitrogen;
(b) formation of amorphous silicon membrane: use plasma enhanced chemical vapor deposition (PECVD) method on above-mentioned substrate, to deposit one deck amorphous silicon (a-Si:H) film; The about 100-500nm of film thickness; Substrate temperature is 250 ℃ during deposition, and the source of the gas of use is 99.999% silane (SiH
4) and hydrogen (H
2), the air pressure range of gas glow discharge is 50-200Pa, radio-frequency voltage is 13.56MHz;
(c) formation of silica membrane: the good amorphous silicon membrane sample of will growing is placed in the oxygen room 20-200 ℃ of following oxidation 0.5 hour-72 hours, thereby forms the silica membrane of the about 1-20nm of one deck;
(d) deposited metal: take out behind the sample with vacuum vapor deposition method or magnetron sputtering method at the metallic copper film of the about 5-100nm of sample surfaces deposit one layer thickness, obtain substrate/a-Si:H/SiO
2/ Cu structure, wherein evaporation or sputter raw material are 99.999% copper powder or copper targets;
(e) then sample being placed with nitrogen is that protection gas, vacuum degree are the cycle annealing stove of 1-10Pa, and cycle annealing was handled 1-2 hour under 250 ℃ of-450 ℃ of conditions, and with sample natural cooling in annealing furnace;
(f) sample after will annealing places corrosive liquid (phosphoric acid: acetic acid: nitric acid: hydrofluoric acid: after deionized water=70%:5%:5%:5%:15%) copper of remained on surface is removed in corrosion; Dry up with nitrogen, the annealing furnace of putting into 450-650 ℃ carried out constant temperature 2-6 hour;
(g) will be once more sample after the annealing in process place corrosive liquid (phosphoric acid: acetic acid: nitric acid: hydrofluoric acid: the immersion 10s of deionized water=70%:5%:5%:5%:15%); Remove the metallic copper that separate out on the surface, and dry up the polysilicon membrane that can make the metallic copper revulsive crystallization at last with nitrogen.
The present invention compares the advantage with other metal inducing crystallization polycrystalline silicon films:
A. can prepare the polysilicon membrane of crystallite dimension in the very fast time at a lower temperature at 50nm-200nm.
B. because the introduction of circulating annealing way has reduced the degree that metallic copper pollutes.
C. because the introducing of copper makes the compatibility of the technology that this invention and semiconductor are made promote.
D. prolonging annealing time is of value to the generation of the polycrysalline silcon of big crystal grain, helps reducing crystal boundary density.
Description of drawings
Fig. 1 is the detection XRD figure of the polysilicon membrane of present embodiment scheme preparation
(a) is the XRD figure spectrum of the film after common metal revulsive crystallization (MIC) is handled among the figure; (b) for composing through circulating annealed copper induced crystallized polycrystalline silicon film XRD figure.
Fig. 2 is the Raman diffused light spectrogram of the polysilicon membrane of present embodiment scheme preparation.
Embodiment
Combine at present accompanying drawing with specific embodiment of the present invention further specify as after.
Embodiment
Process and step in the embodiment of the invention are following:
(1) a common corning glass is cut into 1cm * 1cm size,, be placed on acetone, absolute ethyl alcohol and deionized water for ultrasonic ripple then respectively and cleaned 15 minutes, and dry up with nitrogen with TritonX solvent clean surface dirt;
(2) use plasma-reinforced chemical deposition (PECVD) method on the substrate that cleans up, to deposit one deck amorphous silicon (a-Si:H) film, thickness is about 300nm, and underlayer temperature is 250 ℃ during deposition, and deposition pressure is 10
-5Pa, gas aura air pressure range 50Pa-200Pa, radio-frequency power supply 13.56MHz, source of the gas are that purity is 99.999% silane (SiH
4), the hydrogen purity of using as diluted silane is 5N (99.999%), wherein H
2Shared ratio of gas mixture is about 2%;
(3) the good amorphous silicon membrane sample of will growing is placed on normal temperature oxidation 5h in the oxygen room, puts into the magnetron sputtering vacuum chamber, at the copper film of amorphous silicon surfaces sputter one deck 10nm.Copper target purity 5N (99.999%) wherein, pressure in vacuum tank 10
-5Below the Pa, argon flow amount 7.5sccm during sputter, sputtering chamber pressure is about 0.6Pa, obtains glass/a-Si:H/SiO
2/ Cu structure;
(4) take out glass/amorphous silicon (a-Si:H)/silicon dioxide (SiO
2The sample of)/copper film structure is heat-treated, and puts into vacuum heat treatment furnace, is evacuated to 10
-2Feed nitrogen after the Pa, nitrogen flow is 3SLM, and stability of flow is retreated the invariablenes pressure of liquid of stove at 2.5Pa, and annealing in process lets sample in annealing furnace, naturally cool to room temperature about 1 hour then under 250 ℃ of-450 ℃ of conditions;
(5) after the sample after will annealing places the corrosive liquid corrosion to remove the copper of remained on surface, dry up, put into once more in the annealing furnace, the same step of annealing furnace condition (4), constant temperature 4 hours under 500 ℃ condition then with nitrogen;
(6) place corrosive liquid to soak 10s once more in the sample after the annealing in process, remove the metallic copper that separate out on the surface, can make the polysilicon membrane of metallic copper revulsive crystallization at last.
The obtained sample of this instance uses D/max type X-ray diffractometer to detect; It is as shown in Figure 1 to record the result; Wherein (a) line representes not pass through the XRD figure line of the gained sample of annealing for the second time; And (b) line is represented the XRD figure line through twice cycle annealing gained sample, and the silicon features peak (111) of 28.47o and the characteristic peak (220) of 47.30o have obviously appearred in this figure line.Fig. 2 is the Raman collection of illustrative plates through circulating annealing, and is visible at 520.97cm by figure
-1Stronger Raman peaks spectrum occurred, and the characteristic peak of crystalline silicon is at 520cm
-1, the characteristic peak of amorphous silicon is at 480cm
-1, this shows can be so that amorphous silicon reaches complete crystallization through the method, and 0.97cm occurred
-1Skew possibly be because there is the cause of internal stress in film inside.
Claims (1)
- One kind to induce the amorphous silicon membrane crystallization at low temperatures with metallic copper be the method for polysilicon membrane, it is characterized in that having following process and step:(a) cleaning of substrate glass: at first use the surperficial dirt of TritonX solvent clean glass substrate, be placed on acetone, absolute ethyl alcohol and deionized water for ultrasonic ripple then respectively and cleaned 15 minutes, and dry up with nitrogen;(b) formation of amorphous silicon membrane: use plasma enhanced chemical vapor deposition (PECVD) method on above-mentioned substrate, to deposit one deck amorphous silicon (a-Si:H) film; The about 100-500nm of film thickness; Substrate temperature is 250 ℃ during deposition, and the source of the gas of use is 99.999% silane (SiH 4) and hydrogen (H 2), the air pressure range of gas glow discharge is 50-200Pa, the radio-frequency power supply frequency is 13.56MHz;(c) formation of silica membrane: the good amorphous silicon membrane sample of will growing places oxygen room 20-200 ℃ of following oxidation 0.5 hour-72 hours, thereby forms the silica membrane of the about 1-20nm of one deck;(d) deposited metal: use the metallic copper film of vacuum vapor deposition method or the about 5-100nm of magnetron sputtering method deposit one layer thickness behind the taking-up sample in the above, finally obtain glass/a-Si:H/SiO 2The film sample of/Cu structure; Use therein raw material is 99.999% copper powder or copper target;(e) then sample being placed with nitrogen is that protection gas, vacuum degree are the cycle annealing stove of 1-10Pa, and cycle annealing was handled 1-2 hour under 250 ℃ of-450 ℃ of conditions, and lets sample natural cooling in annealing furnace;(f) sample after will annealing places corrosive liquid (phosphoric acid: acetic acid: nitric acid: hydrofluoric acid: after deionized water=70%:5%:5%:5%:15%) copper of remained on surface is removed in corrosion; Dry up with nitrogen, the annealing furnace of putting into 450-650 ℃ carried out constant temperature 2-6 hour;(g) will be once more sample after the annealing in process place corrosive liquid (phosphoric acid: acetic acid: nitric acid: hydrofluoric acid: the immersion 10s of deionized water=70%:5%:5%:5%:15%); Remove the metallic copper that separate out on the surface, and dry up the polysilicon membrane that can make the metallic copper revulsive crystallization at last with nitrogen.
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Cited By (5)
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| CN103311105A (en) * | 2013-05-16 | 2013-09-18 | 上海大学 | Method for inducing crystallization of amorphous silicon thin film into polycrystalline silicon thin film by aluminum at low temperature |
| CN103708413A (en) * | 2013-12-27 | 2014-04-09 | 安徽师范大学 | Method for preparing one-dimensional silicon nanostructure array on surface of optical fiber |
| CN110760925A (en) * | 2019-11-15 | 2020-02-07 | 常州时创能源科技有限公司 | Method for depositing amorphous silicon thin film by PECVD and application thereof |
| CN112310233A (en) * | 2020-10-16 | 2021-02-02 | 泰州隆基乐叶光伏科技有限公司 | Solar cell, production method and cell module |
| CN112442669A (en) * | 2020-11-23 | 2021-03-05 | 南京工程学院 | Preparation method of self-cleaning antireflection film |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103311105A (en) * | 2013-05-16 | 2013-09-18 | 上海大学 | Method for inducing crystallization of amorphous silicon thin film into polycrystalline silicon thin film by aluminum at low temperature |
| CN103708413A (en) * | 2013-12-27 | 2014-04-09 | 安徽师范大学 | Method for preparing one-dimensional silicon nanostructure array on surface of optical fiber |
| CN103708413B (en) * | 2013-12-27 | 2016-08-17 | 安徽师范大学 | A kind of method preparing one-dimensional silicon nanostructure array at optical fiber surface |
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| CN112310233A (en) * | 2020-10-16 | 2021-02-02 | 泰州隆基乐叶光伏科技有限公司 | Solar cell, production method and cell module |
| CN112310233B (en) * | 2020-10-16 | 2022-06-14 | 泰州隆基乐叶光伏科技有限公司 | Solar cell, production method and cell module |
| CN112442669A (en) * | 2020-11-23 | 2021-03-05 | 南京工程学院 | Preparation method of self-cleaning antireflection film |
| CN112442669B (en) * | 2020-11-23 | 2022-09-23 | 南京工程学院 | Preparation method of self-cleaning antireflection film |
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Application publication date: 20121003 |