CN107516692A - The method and solar cell of deposit dielectrics film on a silicon substrate - Google Patents
The method and solar cell of deposit dielectrics film on a silicon substrate Download PDFInfo
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- CN107516692A CN107516692A CN201610431569.2A CN201610431569A CN107516692A CN 107516692 A CN107516692 A CN 107516692A CN 201610431569 A CN201610431569 A CN 201610431569A CN 107516692 A CN107516692 A CN 107516692A
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 110
- 239000010703 silicon Substances 0.000 title claims abstract description 110
- 239000000758 substrate Substances 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 64
- 239000003989 dielectric material Substances 0.000 title claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000004140 cleaning Methods 0.000 claims abstract description 17
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- ZLOKVAIRQVQRGC-UHFFFAOYSA-N CN(C)[Ti] Chemical compound CN(C)[Ti] ZLOKVAIRQVQRGC-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 7
- 230000009466 transformation Effects 0.000 abstract description 3
- 238000002310 reflectometry Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 56
- 239000010410 layer Substances 0.000 description 43
- 210000004027 cell Anatomy 0.000 description 32
- 238000002161 passivation Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000000415 inactivating effect Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000003071 parasitic effect Effects 0.000 description 2
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 description 1
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 1
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 1
- PXSHDOMYSLTUTJ-UHFFFAOYSA-N [Ti]N Chemical compound [Ti]N PXSHDOMYSLTUTJ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1868—Passivation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02186—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing titanium, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02269—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by thermal evaporation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electromagnetism (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention proposes the solar cell that a kind of methods and applications this method of film of deposit dielectrics on a silicon substrate obtains.This method includes：Clean the surface of silicon substrate；On the surface of silicon substrate by atomic layer deposition method deposit dielectrics film, in temperature T1 less than 350 degrees Celsius of lower circulate operation following steps until thin dielectric film reaches a predetermined thickness D1：Sustainable supply titaniferous compound of reaction, the homogeneous surface for being covered in silicon substrate of titaniferous compound of reaction, the duration t1 of sustainable supply titaniferous compound of reaction are made by atomic layer deposition method；First time nitrogen cleans, cleaning duration t2.The solar cell that methods and applications this method of the film of deposit dielectrics on a silicon substrate provided by the invention obtains, the surface of silicon substrate can be effectively passivated, reduce surface reflectivity, the production technology of silicon solar cell is simplified while the photoelectric transformation efficiency of silicon solar cell is improved, reduces production cost.
Description
Technical field
The present invention relates to the technical field of silicon solar cell, more particularly to a kind of deposit dielectrics film on a silicon substrate
Methods and applications this method obtain solar cell.
Background technology
Recent people gradually recognize that the key factor for improving crystal silicon solar batteries efficiency is to reduce battery surface
Carrier recombination loses.One of most efficient method is by covering one layer of suitable dielectric material on the surface of solar cell
The defects of material is to reduce silion cell surface silicon density, and then reduction carrier is compound by defect near surface, so as to reach
The purpose on surface " passivation ".In recent years, the solar cell of passivation on double surfaces dielectric film is possessed, for example " emitter stage is passivated drawn game
Portion's back contacts " battery (PERC) and " emitter stage is passivated and back perfect diffusion " battery (PERT), gradually by photovoltaic industry
The accreditation on boundary, and production capacity gradually expands.
Dielectric substance for surface passivation has thermal oxidation silicon, plasma reinforced chemical vapour deposition silicon nitride, oxidation
Aluminium and non-crystalline silicon etc., the performance of these dielectric substances are as follows：
1. although thermal oxidation silicon usually requires (to be more than 900 degrees Celsius) at high temperature with excellent inactivating performance
Growth.High-temperature technology can increase the production cost of battery, while cause the performance degradation of low-purity silicon materials (such as polysilicon).
2. silicon nitride has excellent passivation effect for n-type silicon surface, its passivation depends on material middle and high concentration
Positive charge.But when p-type silicon surface is passivated, the positive charge in silicon nitride can be assembled in silicon face and be formed by electronics
Inversion layer.Electrons flow to the local compound of metal contact by inversion layer, form parasitic parallel resistance, reduce battery
Efficiency.
3. aluminum oxide has excellent passivation effect for p-type silicon surface.It is about 1.7 to but have the disadvantage that its refractive index,
Less than the optimal value of silion cell antireflective coating 2.0.So aluminum oxide during surface passivation for also needing to by another high refraction
The dielectric substance of rate is covered, so as to reach suitable optical characteristics and stable electrology characteristic.
4. non-crystalline silicon being capable of very effective passivation n-type and p-type silicon surface.But absorption of the non-crystalline silicon to visible ray
By force, limit it and be used for the application on the preceding surface of solar energy.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of methods and applications of the film of deposit dielectrics on a silicon substrate
The solar cell that this method obtains, silicon solar electricity is simplified while the photoelectric transformation efficiency of silicon solar cell is improved
The production technology in pond, reduce production cost.
In order to solve the above technical problems, the present invention provides a kind of method of the film of deposit dielectrics on a silicon substrate, including：
Clean the surface of the silicon substrate；
It is predetermined by atomic layer deposition method deposition one on the surface of the silicon substrate in the case where temperature T1 is less than 350 degrees Celsius
The thickness D1 thin dielectric film, comprises the following steps：
2.1 sustainable supply titaniferous compound of reactions, make the titaniferous compound of reaction is homogeneous to cover by atomic layer deposition method
Cover in the surface of the silicon substrate, the duration t1 of titaniferous compound of reaction described in sustainable supply；
2.2 first time nitrogen clean, cleaning duration t2；
2.3 under oxidant atmosphere, the titaniferous compound of reaction is oxidized to high price titanium oxide, duration
t3；
2.4 second of nitrogen cleaning, cleaning duration t4；
2.5 reach predetermined thickness D1 when the thin dielectric film, then complete the deposition of the thin dielectric film；When the electricity
Dielectric film is not up to predetermined thickness D1, returns to step 2.1；
Wherein, 10ms≤t1≤1000ms, 100ms≤t2, t4≤2000ms, 10ms≤t3≤500ms.
According to one embodiment of present invention, the predetermined thickness D1 is 50nm~150nm.
According to one embodiment of present invention, the silicon substrate is monocrystalline substrate or multicrystalline silicon substrate.
According to one embodiment of present invention, the titaniferous compound of reaction is titanium tetrachloride, isopropyl titanate and dimethyl
One or more in amino titanium.
According to one embodiment of present invention, the oxidant used middle under oxidant atmosphere is oxygen, deionization
One or more in the oxygen radical of water, ozone and plasma state.
According to one embodiment of present invention, 10ms≤t1≤100ms, 500ms≤t2, t4≤1000ms, 50ms≤t3
≤200ms。
According to one embodiment of present invention, T1 is less than or equal to 150 degrees Celsius.
Present invention also offers a kind of solar cell, including the table of silicon substrate and the phototropic face positioned at the silicon substrate
The back layer of surface layer and/or shady face positioned at the silicon substrate, the superficial layer and/or the back layer include at least one layer
Thin dielectric film, the thin dielectric film are deposited on the silicon substrate by foregoing any method.
The sun that a kind of methods and applications this method of film of deposit dielectrics on a silicon substrate provided by the invention obtains
Energy battery, contains titanium oxide in the thin dielectric film, can effectively be passivated the surface of silicon substrate, is improving silicon solar cell
Photoelectric transformation efficiency while simplify the production technology of silicon solar cell, reduce production cost.
Brief description of the drawings
It is that they are included and form the part of the application to provide further understanding of the invention including accompanying drawing,
Accompanying drawing shows embodiments of the invention, and plays a part of the explanation principle of the invention together with this specification.In accompanying drawing：
Fig. 1 shows the FB(flow block) of the method for deposit dielectrics film on a silicon substrate of the invention.
Fig. 2 shows the FB(flow block) of the specific steps of the method for deposit dielectrics film on a silicon substrate of the invention.
Fig. 3 shows the structural representation of one embodiment of the solar cell of the present invention.
Fig. 4 shows the structural representation of another embodiment of the solar cell of the present invention.
Embodiment
Embodiments of the invention are described with detailed reference to accompanying drawing now.In the case of any possible, in all of the figs
It will be marked using identical to represent same or analogous part.In addition, although the term used in the present invention is from known
Selected in public term, but some terms mentioned in description of the invention are probably applicant to be sentenced as his or her
Break and carry out selection, its detailed meanings illustrates in the relevant portion of description herein.In addition, it is desirable to not only by used
Actual terms, and the meaning that is also to be contained by each term understands the present invention.
Due to suitable refractive index and the Weak Absorption to visible ray, titanium dioxide is in generation 1970 to nineteen ninety by as one
Kind optics antireflection film material, is widely used in the industrial production of screen-printed solar cell.Titanium dioxide can be used
A variety of preparation methods are realized, such as sputtering, thermal evaporation, spin coating, cracking, aumospheric pressure cvd and ald.In early days
The ability of titanium dioxide surface passivation is poor.Surface passivation is generally required by the lamination of titanium dioxide and thermal oxidation silicon come real
It is existing.
Method provided by the invention is to consider to deposit the electricity containing titanium oxide by atomic layer deposition method on a silicon substrate
Dielectric film, make the dielectric film can the preceding surface as silicon substrate or the rear surface as silicon substrate, possess compared with
Good optically and electrically attribute.
Fig. 1 shows the FB(flow block) of the method for deposit dielectrics film on a silicon substrate of the invention.Fig. 2 shows this hair
The FB(flow block) of the specific steps of the method for the bright film of deposit dielectrics on a silicon substrate.As illustrated, one kind is on a silicon substrate
The method of deposit dielectrics film, including following two steps：
Step 101, the surface of silicon substrate is cleaned.The surface of silicon substrate needs thoroughly cleaning, it is ensured that surface does not have any to have
It may interfere with the impurity and residue of thin dielectric film deposition.The silicon substrate can be monocrystalline substrate or multicrystalline silicon substrate.Tool
For body, during the surface of cleaning silicon substrate, the industry cleaning link method that can be selected includes RCA (Radio
Corporation America), the one or more in HF/HCl, O3/HF etc..Wherein RCA standard cleanings method is a kind of wet
Formula chemical cleaning method.It is unrestricted as an example, the surface of silicon substrate is cleaned using RCA standard cleanings method first, its
The oxide of surface of silicon is removed by hydrofluoric acid afterwards.This process can go the removal of impurity and residue, so as to thoroughly clear
The surface of clean silicon substrate.
Step 102, in the case where temperature T1 is less than 350 degrees Celsius, deposited on the surface of silicon substrate by atomic layer deposition method
One predetermined thickness D1 thin dielectric film.Wherein predetermined thickness D1 scope can be 50nm~150nm, and nm here refers to receive
Rice.The predetermined thickness D1 of thin dielectric film depends on the refractive index of prepared thin dielectric film.
Step 102 comprises the following steps：
Step 201, sustainable supply titaniferous compound of reaction, make titaniferous compound of reaction is homogeneous to cover by atomic layer deposition method
Cover in the surface of silicon substrate, the duration t1 of sustainable supply titaniferous compound of reaction；
Step 202, first time nitrogen cleans, cleaning duration t2；
Step 203, under oxidant atmosphere, titaniferous compound of reaction is made to be oxidized to high price titanium oxide, duration
t3；
Step 204, second of nitrogen cleaning, cleaning duration t4；
Step 205, when thin dielectric film reaches predetermined thickness D1, then entrance terminates 206, completes the heavy of thin dielectric film
Product；When thin dielectric film is not up to predetermined thickness D1, step 201 is returned to；
Wherein, 10ms≤t1≤1000ms, 100ms≤t2, t4≤2000ms, 10ms≤t3≤500ms, ms refer to millisecond.
It should be noted that homogeneous (uniformity) degree that titaniferous compound of reaction covers in atomic layer deposition process is logical
Cross voltage input supply valve (including titaniferous compound of reaction supply valve and oxidant atmosphere supply valve) and the switch of nitrogen purge valve
Time controls.With ensure titaniferous compound of reaction can when supply valve is opened homogeneous covering surface of silicon, it is while excessive
Titaniferous compound of reaction be cleaned before the closing of nitrogen purge valve, therefore voltage input supply valve and nitrogen purge valve
Switch time is the key of fine and close, high quality the titanium oxide of ald.Specifically, sustainable supply titaniferous reaction chemical combination
The duration t1 of thing just refers to the supply valve switch time of titaniferous compound of reaction, and t1 should be in 10-1000 milliseconds；Oxidant atmosphere
Duration t3 just refers to that the supply valve open period t3 of oxidant atmosphere should be in 10-500 milliseconds；For the first time, second of nitrogen
Cleaning duration t2 and t4 refer to the time that nitrogen purge valve is opened, it should which control is in 100-2000 milliseconds.
Described in connecting, before this layer of thin dielectric film that the surface of silicon substrate is formed can be used for silicon solar cell
Surface and rear surface.When for preceding surface, thin dielectric film can be used as surface passivation material or be used as light
Learn antireflection layer.Pass through the process conditions for the method for controlling deposit dielectrics film, such as temperature, deposition cycle operation cycle
Number so that the thickness control of the thin dielectric film is between 50-150 nanometers, the refractive index of the thin dielectric film required for obtaining.
After thin dielectric film is used for when surface, the thin dielectric film can be used as surface passivation material or back reflection layer.Work as length
The light (such as infrared light) of wavelength can be reflected by this thin dielectric film later through solar cell, so as to increase light
Stroke in solar cells.Identical with the preceding surface for silicon solar cell, the thickness control of the thin dielectric film exists
Between 50-150 nanometers, so as to obtain the refractive index of required thin dielectric film.
In the method for atomic layer deposition method deposit dielectrics film, titaniferous compound of reaction first contacts silicon substrate, and
One is covered in the surface of silicon substrate, and high price titanium oxide is oxidized under oxidant atmosphere.Wherein used titaniferous reaction
Compound can be the one or more in titanium tetrachloride, isopropyl titanate and dimethylamino titanium.
The oxidant used in oxidant atmosphere in the method for atomic layer deposition method deposit dielectrics film can be
Oxygen, deionized water, ozone and plasma state oxygen radical in one or more.
It is preferred that 10ms≤t1≤100ms, 500ms≤t2, t4≤1000ms, 50ms≤t3≤200ms.
On the other hand, the crystalline state of the titanium oxide formed in thin dielectric film can change with the rise of depositing temperature.
Therefore T1 should be less than 350 degrees Celsius.More preferably, T1 is less than or equal to 150 degrees Celsius.
The method of film of deposit dielectrics on a silicon substrate provided by the invention a kind of and existing surface passivation technology and
Method compares, and has following features：
1. excellent inactivating performance can be realized by relatively low technological temperature, so as to reduce preparation cost；
2. silicon face will not form inversion layer when being passivated p-type material, it is lost from without parasitic parallel resistance；
3. undoped n-type and p-type silicon surface can be passivated, and the p+ silicon faces of heavy doping；
4. it need not expose, the subsequent technique such as annealing；
5. single thin film material can both be used as surface passivation material as optics antireflection layer or simultaneously, simplify solar energy
The preparation technology of battery.
Present invention also offers a kind of solar cell.This kind of solar cell includes silicon substrate and served as a contrast positioned at the silicon
The back layer of the superficial layer of the phototropic face at bottom and/or shady face positioned at the silicon substrate, the superficial layer and/or the back layer bag
At least one layer of thin dielectric film is included, the thin dielectric film is deposited on a silicon substrate by any of the above-described kind of method.
Fig. 2 shows the structural representation of one embodiment of the solar cell of the present invention.A kind of as illustrated, p-type
Silicon solar cell 100 includes silicon substrate 107.The silicon substrate 107 includes the substrate 104 of p-type element doping and is arranged on substrate
The emitter stage 103 by n-type element doping on 104.Superficial layer 102 is located at the phototropic face of silicon substrate 107, i.e., positioned at emitter stage
On 103.Here superficial layer 102 includes at least one layer of thin dielectric film, using method provided by the invention in silicon substrate 107
The thin dielectric film is deposited by atomic layer deposition method on phototropic face, the thin dielectric film contains titanium oxide.Superficial layer 102 was both
Can be as the surface passivation material of p-type silicon solar cell 100, while optics antireflection layer can also be used as.Back layer 105
Positioned at the shady face of silicon substrate 107.Similar, back layer 105 here includes at least one layer of thin dielectric film, using the present invention
The method of offer deposits the thin dielectric film on the shady face of silicon substrate 107 by atomic layer deposition method, the thin dielectric film
Contain titanium oxide.Back layer 105 both can be as the surface passivation material of p-type silicon solar cell 100, while can also make
For back reflection layer.The front surface electrode 101 of p-type silicon solar cell 100 contacts through superficial layer 102 with silicon substrate 107.P-type
The backplate 106 of silicon solar cell 100 contacts through back layer 105 with silicon substrate 107.
Fig. 3 shows the structural representation of another embodiment of the solar cell of the present invention.A kind of as illustrated, n
Type silicon solar cell 200 includes silicon substrate 208.The silicon substrate 208 is including the substrate 204 by n-type element doping and is arranged on
The emitter stage 203 by p-type element doping in substrate 204, and the contact layer 205 by n-type element heavy doping.Superficial layer 202
Positioned at the phototropic face of silicon substrate 208, i.e., on emitter stage 203.Here superficial layer 202 includes at least one layer of thin dielectric
Film, the thin dielectric film is deposited by atomic layer deposition method on the phototropic face of silicon substrate 208 using method provided by the invention,
The thin dielectric film contains titanium oxide.Superficial layer 202 both can as the surface passivation material of n-type silicon solar cell 200,
Optics antireflection layer can also be used as simultaneously.Back layer 206 is located at the shady face of silicon substrate 208, i.e. one close to contact layer 205
Side.Similar, back layer 206 here includes at least one layer of thin dielectric film, using method provided by the invention in silicon substrate
The thin dielectric film is deposited by atomic layer deposition method on 208 shady face, the thin dielectric film contains titanium oxide.Back layer
206 both can be as the surface passivation material of n-type silicon solar cell 200, while can also be used as back reflection layer.N-type silicon is too
The front surface electrode 201 of positive energy battery 200 contacts through superficial layer 202 with silicon substrate 208.The back of the body of n-type silicon solar cell 200
Face electrode 207 contacts through back layer 206 with silicon substrate 208.
Those skilled in the art can be obvious, can to the present invention above-mentioned example embodiment carry out various modifications and variations and
Without departing from the spirit and scope of the present invention.Accordingly, it is intended to present invention covering is set to fall in appended claims and its equivalence techniques
Modifications of the present invention and modification in aspects.
Claims (8)
1. a kind of method of the film of deposit dielectrics on a silicon substrate, including：
Clean the surface of the silicon substrate；
In the case where temperature T1 is less than 350 degrees Celsius, one predetermined thickness is deposited by atomic layer deposition method on the surface of the silicon substrate
The D1 thin dielectric film, comprises the following steps：
2.1 sustainable supply titaniferous compound of reactions, make the titaniferous compound of reaction is homogeneous to be covered in by atomic layer deposition method
The surface of the silicon substrate, the duration t1 of titaniferous compound of reaction described in sustainable supply；
2.2 first time nitrogen clean, cleaning duration t2；
2.3 under oxidant atmosphere, the titaniferous compound of reaction is oxidized to high price titanium oxide, duration t3；
2.4 second of nitrogen cleaning, cleaning duration t4；
2.5 reach predetermined thickness D1 when the thin dielectric film, then complete the deposition of the thin dielectric film；When the dielectric
Film is not up to predetermined thickness D1, returns to step 2.1；
Wherein, 10ms≤t1≤1000ms, 100ms≤t2, t4≤2000ms, 10ms≤t3≤500ms.
2. a kind of method of the film of deposit dielectrics on a silicon substrate as claimed in claim 1, it is characterised in that described predetermined
Thickness D1 is 50nm~150nm.
A kind of 3. method of the film of deposit dielectrics on a silicon substrate as claimed in claim 1, it is characterised in that the silicon lining
Bottom is monocrystalline substrate or multicrystalline silicon substrate.
A kind of 4. method of the film of deposit dielectrics on a silicon substrate as claimed in claim 1, it is characterised in that the titaniferous
Compound of reaction is the one or more in titanium tetrachloride, isopropyl titanate and dimethylamino titanium.
5. a kind of method of the film of deposit dielectrics on a silicon substrate as claimed in claim 1, it is characterised in that described in oxygen
The middle oxidant that uses is one kind or several in the oxygen radical of oxygen, deionized water, ozone and plasma state under agent atmosphere
Kind.
A kind of 6. method of the film of deposit dielectrics on a silicon substrate as claimed in claim 1, it is characterised in that 10ms≤t1
≤ 100ms, 500ms≤t2, t4≤1000ms, 50ms≤t3≤200ms.
7. a kind of method of the film of deposit dielectrics on a silicon substrate as claimed in claim 1, it is characterised in that T1 is less than etc.
In 150 degrees Celsius.
8. a kind of solar cell, including silicon substrate and positioned at the silicon substrate phototropic face superficial layer and/or positioned at institute
The back layer of the shady face of silicon substrate is stated, the superficial layer and/or the back layer include at least one layer of thin dielectric film, described
Thin dielectric film by any method as described in claim 1-7 be deposited on as described on silicon substrate.
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