CN102296363A - Method for depositing microcrystalline silicon thin film - Google Patents
Method for depositing microcrystalline silicon thin film Download PDFInfo
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- CN102296363A CN102296363A CN201010206866XA CN201010206866A CN102296363A CN 102296363 A CN102296363 A CN 102296363A CN 201010206866X A CN201010206866X A CN 201010206866XA CN 201010206866 A CN201010206866 A CN 201010206866A CN 102296363 A CN102296363 A CN 102296363A
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Abstract
The invention belongs to the field of semiconductor materials, discloses a method for depositing a microcrystalline silicon thin film, and particularly relates to a method for preparing a thin microcrystalline silicon layer on an amorphous silicon thin film surface, which is deposited on a glass substrate, by using a laser surface crystallization method. The method comprises a step of: partially converting an amorphous silicon thin film which is directly deposited on a glass plate into microcrystalline silicon by using a laser heating crystallization method, wherein the used laser heating crystallization method comprises the following steps of: placing an amorphous silicon thin film sample on a sample table of a laser; irradiating with a laser beam; converting the energy of the laser absorbed by the amorphous silicon thin film into energy of the amorphous silicon thin film; performing partial melting re-crystallization; and performing surface crystallization treatment to convert the amorphous silicon into microcrystalline silicon. By adopting the method, the problems of low growth rate, low crystallization degree, low mobility, low photoelectric conversion efficiency and the like existing in the prior art can be solved; and the microcrystalline silicon thin film which is crystallized by using excimer laser has the advantages of high degree of crystallization, uniform grain, capability of realizing large-area low-temperature preparation, short process period and the like.
Description
Technical field:
The invention belongs to field of semiconductor materials, is a kind of preparation method of microcrystalline silicon film.Specifically be that sedimentary non-crystalline silicon (a-Si) film surface adopts the method for laser surface crystallization to prepare the method for skim microcrystal silicon (μ c-Si) layer on glass substrate.
Background technology:
As the silicon-film solar-cell of s-generation solar cell because have the starting material abundance, composition is cheap, energy consumption is low, be easy to large-scale production or the like advantage, has obtained widespread use in industrial production.Silicon film mainly comprises non-crystalline silicon, microcrystal silicon and polysilicon membrane.Wherein, microcrystalline silicon film is a kind of mixed phase disordered semiconductor material between non-crystalline silicon and silicon single crystal, both had the stable optical property of silicon single crystal, the high absorption coefficient characteristic of non-crystalline silicon is arranged again, and higher specific conductivity, no obvious photo attenuation phenomenon are arranged, easily realize advantages such as large-area preparation, the stability that helps improving battery, extending battery life.Constantly improve and the market fast development from thin film technique, the microcrystalline silicon film battery is considered to most possibly replace the solar cell of future generation of monocrystalline silicon battery and amorphous silicon membrane battery, has now become the research focus of international field of solar energy.
At present, the preparation method of microcrystalline silicon film is direct sedimentation, comprises that radio frequency plasma strengthens chemical vapour deposition (RF-PECVD), hot-wire chemical gas-phase deposition (HWCVD) and very high frequency(VHF) plasma reinforced chemical vapour deposition (VHF-PECVD).
Very high frequency(VHF) plasma reinforced chemical vapour deposition (VHF-PECVD) method is with H
2The SiH of dilution
4Gas is source gas, and underlayer temperature uses traditional plasma reinforced chemical vapour deposition (PECVD) equipment, with the direct formation of deposits microcrystalline silicon film of the excitation of plasma frequency of 60～90MHz between 250～400 ℃.The problem that this method exists when preparing microcrystalline silicon film is that growth velocity is lower
Be unfavorable for reducing manufacturing cost.
Hot-wire chemical gas-phase deposition (HWCVD) method is with H
2The SiH of dilution
4Or Si
2H
6Gas by pyritous wire (normally tungsten), is deposited on after being decomposed and forms microcrystalline silicon film on the substrate earlier.The metal ion pollution problem is also unresolved in the microcrystalline silicon film of this method preparation.
Radio frequency PECVD method is with H
2The SiH of dilution
4Gas is source gas, and underlayer temperature uses traditional plasma reinforced chemical vapour deposition (PECVD) equipment, usually with 13.56MHz frequency activated plasma, to form microcrystalline silicon film on substrate between 250～400 ℃.This technology is cheap owing to equipment, and technology maturation is good with other industrial technology compatibility, have the certain development potentiality, but its sedimentation rate is lower
Electron cyclotron resonance chemical vapor deposition (ECR CVD) method is with H
2The SiH of dilution
4Gas is source gas, utilize high-density plasma stream near the substrate the ECR plasma zone depositing silicon atom to form microcrystalline silicon film.
The direct sedimentation of above-mentioned usefulness prepares microcrystalline silicon film, and have following problem in varying degrees: growth velocity is low, is unfavorable for reducing manufacturing cost; Degree of crystallinity is low, and about 50%; Mobility is low, and photoelectric transformation efficiency is low.
Summary of the invention
In order to overcome the shortcoming that above direct deposition prepares the microcrystalline silicon film method, the present invention is the predecessor with direct sedimentary amorphous silicon membrane, method by the LASER HEATING crystallization changes amorphous silicon membrane into microcrystalline silicon film, and purpose provides a kind of preparation method of microcrystalline silicon film.
Technical scheme of the present invention is:
A kind of deposition method of microcrystalline silicon film with the amorphous silicon membrane that directly is deposited on the sheet glass, makes amorphous silicon membrane partly be converted into microcrystal silicon with the method for LASER HEATING crystallization; The method of used LASER HEATING crystallization is that the amorphous silicon membrane sample is placed on the sample table of laser apparatus, shine with laser beam, the energy transformation that amorphous silicon membrane has absorbed laser is a self-energy, and the local melting recrystallize takes place, and handles making non-crystalline silicon change microcrystal silicon into through surface crystallization.
The deposition method of described microcrystalline silicon film, used laser apparatus are excimer laser, and used working gas is KrF gas or ArF gas, and laser spot size is 30x10mm, and laser pulse width is 10-30ns, and pulse-repetition frequency is 1～50Hz; The single pulse maximum output energy is 1.2J; When working gas was KrF gas, output optical maser wavelength was 248nm; When working gas was ArF gas, output optical maser wavelength was 193nm.
The deposition method of described microcrystalline silicon film, the amorphous silicon membrane sample is fixed on the sample table of excimer laser, and adjustment sample table position makes laser beam can shine sample, working gas KrF gas or ArF will be charged in the laser apparatus, and keep-up pressure and be 0.2-2.0MPa, progressively adjust pumping pulse,, cause F when the pumping pulse of peak value 12～20kV is added between the discharge electrode of casing
2Kr or F
2The discharge of Ar dipolymer molecule stimulated luminescence, output laser energy density scope is 50mJ/cm
2～300mJ/cm
2, then sample being shone, the radiation pulses number is 1～10, the time that laser beam carries out single fraction irradiation is 10-30ns.
The deposition method of described microcrystalline silicon film in the surface crystallization treating processes, at room temperature carries out, and adopts high-purity Ar as shielding gas.
The deposition method of described microcrystalline silicon film, the thickness of microcrystal silicon layer are 100-800nm, and grain-size is 30-100nm.
The invention has the beneficial effects as follows:
1, the present invention utilizes existing non-crystalline silicon maturation process to prepare amorphous silicon membrane on common glass substrates.Then, utilize the laser crystallization technology in a short period of time amorphous silicon material to be heated to very high temperature and make it melt crystallization then, owing to the time can be controlled very shortly, so substrate temperature is unlikely too high, thereby can use cheap glass as substrate.
2, the present invention cleans up the amorphous silicon membrane sample successively with acetone and spirituous solution, sample levels is fixed on the sample table after to be dried.Therefore a-Si film generation oxidative phenomena adopts high-purity Ar as shielding gas when preventing laser crystallization.During experiment laser energy density is set at required value, earlier logical high-purity Ar shielding gas carries out monopulse or multipulse irradiation to pretreated sample then at ambient temperature, and irradiation is closed Ar after finishing, and sample is taken off in the sample sack of packing into preserve.
3, the method for laser crystallization of the present invention is to realize by the excimer laser of routine.Since excimer laser have emission wavelength short-wave band, the pulsewidth of ultraviolet narrower (10～30ns), pulse-repetition frequency reaches as high as advantages such as 300Hz and pulse power are big, and amorphous silicon material is to having very strong absorption characteristic, so excimer laser becomes the preferred light source that industrial low-temperature prepares microcrystalline silicon film.Utilize the microcrystalline silicon film of excimer laser crystallization to have degree of crystallinity height, uniform crystal particles, can realize advantages such as big area low temperature prepares, process cycle is short, therefore have bright development prospect.
4, the deposition method of the used amorphous silicon membrane of the present invention is a lot, comprises low-pressure chemical vapor deposition (LPCVD), plasma reinforced chemical vapour deposition (PECVD), hot-wire chemical gas-phase deposition (HWCVD), electron cyclotron resonance chemical vapor deposition (ECR CVD) or the like.These method technical maturities, sedimentation rate is fast, and the rete densification has overcome the low shortcoming of microcrystalline silicon film sedimentation rate, has reduced cost.
Description of drawings
The pairing film Raman of different laser energy density scattering spectrogram when Fig. 1 shines for monopulse.
Fig. 2 is 250mJ/cm for laser energy density
2After the monopulse irradiation, the cross section FE-SEM pattern of film.
The pairing Raman scattering of different laser energy density spectrogram when Fig. 3 is 10 pulse irradiations.
Embodiment
Specify the present invention below in conjunction with embodiment.
With plasma reinforced chemical vapour deposition (PECVD) method at the thick amorphous silicon membrane of deposition on glass 1.7 μ m.Discharge gas is Ar, and reactant gases is SiH
4Deposition process parameters is: sediment chamber's base vacuum 7 * 10
-3Pa, SiH
4Flow 10sccm, Ar flow 70sccm, depositing temperature～300 ℃, reaction chamber air pressure 3.0Pa, microwave power 600W, depositing time are 6h.
The a-Si film of pre-deposition is successively cleaned with acetone and spirituous solution, be fixed on after the drying on the sample table, prepare to carry out laser surface crystallization.Laser source adopts excimer laser, will charge into working gas KrF in the laser apparatus, and keep-ups pressure and be 0.5MPa; feed the shielding gas of argon gas as workpiece; progressively adjust pumping pulse,, cause F when the pumping pulse of peak value 12～20kV is added between the discharge electrode of casing
2The high-octane laser pulse of final output is amplified in the discharge of Kr dipolymer molecule stimulated luminescence, the resonator cavity that the laser of 248nm wavelength is made up of reflective mirror, discharge tank, optical maser wavelength tuner module.Excimer laser shines on the workpiece after handling through optical system, can pass through mobile lens, the distance of regulating condenser lens and sample is with the laser beam optimization, and by regulating surperficial exposure area to regulate the energy density size, the variation range of energy density is 50mJ/cm
2～300mJ/cm
2(present embodiment is 150mJ/cm
2～250mJ/cm
2), original output facula is of a size of 30x10mm; Laser pulse width is 25ns, and the pulse maximum repetition rate is 50Hz; The single pulse maximum output energy is 1.2J, and the radiation pulses number is 1～10, and the time that laser beam carries out single fraction irradiation is 25ns.The frequency of the energy of excimer laser, pulse number and laser apparatus can be regulated control respectively, and laser radiation finishes the back sample is carried out Raman (Laman) test.
In the surface crystallization treating processes, under room temperature (25 ℃) and air conditions, carry out,, adopt high-purity Ar (more than the 99.99wt%) as shielding gas for preventing amorphous silicon membrane oxidation by air in processing.
As shown in Figure 1, when monopulse shines the pairing film Raman of the different laser energy density scattering spectrogram as can be seen, when laser energy density is increased to 150mJ/cm
2The time, amorphous silicon membrane begins to occur crystallization, and along with the increase of laser energy density, crystallization rate increases gradually, and the crystallization rate scope that calculates from Raman spectrum is 15～72%.
As shown in Figure 2, be 250mJ/cm from laser energy density
2After the monopulse irradiation, the cross section FE-SEM pattern of film as can be seen, the microcrystalline coating thickness of film surface is about 400～500nm, grain-size is 60～110nm, still is non-crystallized amorphous layer below.
As shown in Figure 3, during from 10 pulse irradiations the pairing Raman scattering of the different laser energy density spectrogram as can be seen, when laser energy density surpasses 150mJ/cm
2The time, show that tangible crystallization change has taken place film.Illustrate also whether this film when accepting laser radiation, the size that crystallization change depends primarily on laser energy density takes place, and the not influence of Stimulated Light radiation pulses number.
Embodiment 2
Difference from Example 1 is:
With plasma reinforced chemical vapour deposition (PECVD) method at the thick amorphous silicon membrane of deposition on glass 700nm.Discharge gas is Ar, and reactant gases is SiH
4Deposition process parameters is: sediment chamber's base vacuum 7 * 10
-3Pa, SiH
4Flow 10sccm, Ar flow 70sccm, depositing temperature～300 ℃, reaction chamber air pressure 3.0Pa, microwave power 600W, depositing time are 4h.
The a-Si film of pre-deposition is successively cleaned with acetone and spirituous solution, be fixed on after the drying on the sample table, prepare to carry out laser surface crystallization.Laser source adopts excimer laser, will charge into working gas ArF in the laser apparatus, and keep-ups pressure and be 0.5MPa; feed the shielding gas of argon gas as workpiece; progressively adjust pumping pulse,, cause F when the pumping pulse of peak value 12～20kV is added between the discharge electrode of casing
2The high-octane laser pulse of final output is amplified in the discharge of Ar dipolymer molecule stimulated luminescence, the resonator cavity that the laser of 193nm wavelength is made up of reflective mirror, discharge tank, optical maser wavelength tuner module.Excimer laser shines on the workpiece after handling through optical system, can pass through mobile lens, the distance of regulating condenser lens and sample is with the laser beam optimization, and by regulating surperficial exposure area to regulate the energy density size, the variation range of energy density is 50mJ/cm
2～300mJ/cm
2(present embodiment is 120mJ/cm
2～240mJ/cm
2), original output facula is of a size of 30x10mm; Laser pulse width is 25ns, and the pulse maximum repetition rate is 50Hz; The single pulse maximum output energy is 1.2J, and the radiation pulses number is 5, and the time that laser beam carries out single fraction irradiation is 25ns.The frequency of the energy of excimer laser, pulse number and laser apparatus can be regulated control respectively, and laser radiation finishes the back sample is carried out Raman (Laman) test.
In the present embodiment, the microcrystal silicon of film surface (μ c-Si) layer thickness is about 100～150nm, and grain-size is 30～70nm.
Claims (5)
1. the deposition method of a microcrystalline silicon film is characterized in that: will directly be deposited on the amorphous silicon membrane on the sheet glass, and make amorphous silicon membrane partly be converted into microcrystal silicon with the method for LASER HEATING crystallization; The method of used LASER HEATING crystallization is that the amorphous silicon membrane sample is placed on the sample table of laser apparatus, shine with laser beam, the energy transformation that amorphous silicon membrane has absorbed laser is a self-energy, and the local melting recrystallize takes place, and handles making non-crystalline silicon change microcrystal silicon into through surface crystallization.
2. according to the deposition method of right 1 described microcrystalline silicon film, it is characterized in that: used laser apparatus is an excimer laser, and used working gas is KrF gas or ArF gas, and laser spot size is 30 * 10mm, laser pulse width is 10-30ns, and pulse-repetition frequency is 1～50Hz; The single pulse maximum output energy is 1.2J; When working gas was KrF gas, output optical maser wavelength was 248nm; When working gas was ArF gas, output optical maser wavelength was 193nm.
3. according to the deposition method of right 2 described microcrystalline silicon films, it is characterized in that: the amorphous silicon membrane sample is fixed on the sample table of excimer laser, and adjustment sample table position makes laser beam can shine sample, working gas KrF gas or ArF will be charged in the laser apparatus, and keep-up pressure and be 0.2-2.0MPa, progressively adjust pumping pulse,, cause F when the pumping pulse of peak value 12～20kV is added between the discharge electrode of casing
2Kr or F
2The discharge of Ar dipolymer molecule stimulated luminescence, output laser energy density scope is 50mJ/cm
2～300mJ/cm
2, then sample being shone, the radiation pulses number is 1～10, the time that laser beam carries out single fraction irradiation is 10-30ns.
4. according to the deposition method of right 3 described microcrystalline silicon films, it is characterized in that: in the surface crystallization treating processes, at room temperature carry out, adopt high-purity Ar as shielding gas.
5. according to the deposition method of right 1 described microcrystalline silicon film, it is characterized in that: the thickness of microcrystal silicon layer is 100-800nm, and grain-size is 30-100nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104790032A (en) * | 2015-03-16 | 2015-07-22 | 大连大学 | Method for laser pulse sputtering deposition preparation of polycrystalline silicon thin film |
| CN112382680A (en) * | 2020-10-09 | 2021-02-19 | 浙江爱旭太阳能科技有限公司 | HJT battery and preparation method thereof based on laser induction |
-
2010
- 2010-06-23 CN CN201010206866XA patent/CN102296363A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 《真空》 20090731 崔连武等 "准分子激光引起的非晶硅薄膜晶化行为的研究" 第46卷, 第4期 * |
| 崔连武等: ""准分子激光引起的非晶硅薄膜晶化行为的研究"", 《真空》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104790032A (en) * | 2015-03-16 | 2015-07-22 | 大连大学 | Method for laser pulse sputtering deposition preparation of polycrystalline silicon thin film |
| CN112382680A (en) * | 2020-10-09 | 2021-02-19 | 浙江爱旭太阳能科技有限公司 | HJT battery and preparation method thereof based on laser induction |
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Application publication date: 20111228 |