CN102201461A - Polycrystalline silicon thin film and method for preparing polycrystalline silicon thin film by amorphous silicon low-temperature induction - Google Patents
Polycrystalline silicon thin film and method for preparing polycrystalline silicon thin film by amorphous silicon low-temperature induction Download PDFInfo
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- CN102201461A CN102201461A CN2011101111953A CN201110111195A CN102201461A CN 102201461 A CN102201461 A CN 102201461A CN 2011101111953 A CN2011101111953 A CN 2011101111953A CN 201110111195 A CN201110111195 A CN 201110111195A CN 102201461 A CN102201461 A CN 102201461A
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- amorphous silicon
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Abstract
The invention discloses a method for preparing a polycrystalline silicon thin film by amorphous silicon low-temperature induction, belonging to the technical field of thin-film solar battery. The method overcomes the disadvantage of slow crystallization rate of the existing metal induction method. According to the invention, a titanium silicide nano-wire layer and an amorphous silicon thin film layer are sequentially deposited on a substrate from bottom to top, wherein the titanium silicide nano-wire layer induces the amorphous silicon thin film layer to form a polycrystalline silicon thin film layer, thereby forming a polycrystalline silicon thin film having a three-layer composite structure consisting of the substrate, a transition layer with coexisting titanium silicide nano-wire and polycrystalline silicon thin film, and the polycrystalline silicon thin film layer. On one hand, the crystallization of the amorphous silicon thin film can be induced at a lower crystallization temperature easily since the titanium silicide nano-wire is used as an inducer; on the other hand, the titanium silicide nano-wire with a huge specific surface area can increase the contact area between the induction layer and the amorphous silicon, thereby increasing the nucleation number in the initial crystallization stage of the amorphous silicon and greatly improving the crystallization rate; and the entire crystallization process is completed in 2 to 4 hours.
Description
Technical field
The invention belongs to technical field of thin-film solar, specifically is a kind of polysilicon membrane and the method for preparing polysilicon membrane with the amorphous silicon low temperature induction.
Background technology
Photovoltaic generation is as a kind of important novel renewable green energy resource, by countries in the world broad research and utilization; In numerous solar cells, silica-based solar cell has the advantage of abundant raw material, nonhazardous, becomes the main body in solar cell market, especially polycrystal silicon cell now, the relative advantages of simple of efficient height, production technology and production cost.With the trend of the preferential Battery Market research and development of battery efficiency and production cost, polycrystal silicon cell will move towards filming.At present, have the research for preparing the aspect about polysilicon membrane in a large number, be a challenge of difficulty concerning the researcher yet low temperature prepares large grain size polysilicon film always.Tradition polysilicon membrane preparation method comprises two steps: deposition of amorphous silicon films and amorphous silicon membrane crystallization on substrate.Technology about the amorphous silicon membrane crystallization mainly contains solid phase crystallization method, laser crystallization method; Solid phase crystallization method needs amorphous silicon membrane is carried out the integral body heating, temperature requirement is heated to the melting point (1414 ℃) of silicon, and laser crystallization method equipment cost is higher, and technology is complicated simultaneously, also there is damage in the localized hyperthermia of laser beam to substrate except making recrystallized amorphous silicon.In recent years, a kind of metal-induced crystallization method receives much concern, adopt evaporation and the sputtering method metals such as aluminium, silver or gold of deposition one deck hundreds of nanometer thickness on substrates such as glass earlier in the research, on metal level, deposit one deck amorphous silicon membrane again, then with the film annealing crystallization under 500 to 600 ℃ temperature that deposits.
The metal inducement method has greatly reduced the temperature of amorphous silicon membrane crystallization, and still, 500 to 600 ℃ crystallization temperature has limitation for the selection of substrate.Simultaneously, this crystallization inducing metal method, its mechanism is, polysilicon is forming core on metal level earlier, then these independently nucleus to around growth form one deck crystal until being in contact with one another, this layer crystal body is induced the amorphous silicon crystallization of contact with it again, in this course, only nucleus growth becomes one deck polysilicon crystal just to need about 90 minutes time, so crystalline rate is slower.
Summary of the invention
The technical assignment of the technical problem to be solved in the present invention and proposition is to overcome the existing slower defective of metal inducement method crystalline rate, a kind of polysilicon membrane is provided and prepares the method for polysilicon membrane with the amorphous silicon low temperature induction.
For reaching the object of the invention, polysilicon membrane of the present invention comprises substrate and layer polysilicon film, it is characterized in that: the transition zone that has the coexistence of the titanium silicide nano line that is combined with each other with the two and polysilicon membrane between described substrate and the layer polysilicon film.
Optimization technique measure as described polysilicon membrane: described substrate is the transparent conductive oxide film glass of tin oxide or zinc oxide, or is corrosion resistant plate.Described titanium silicide nano line comprises at least a form in nano wire, nano-nail, nanometer rods, nano line cluster, the rocket shape nano wire.Described titanium silicide nano line is TiSi crystalline phase or TiSi
2Crystalline phase.
For reaching the object of the invention, the method for preparing polysilicon membrane with the amorphous silicon low temperature induction of the present invention, be on substrate, to deposit titanium silicide nano wire layer and amorphous silicon membrane layer from bottom to top successively, induce the crystallization of amorphous silicon membrane layer to become layer polysilicon film by described titanium silicide nano line layer.
As the described optimization technique measure for preparing the method for polysilicon membrane with the amorphous silicon low temperature induction: described substrate is the transparent conductive oxide film glass of tin oxide or zinc oxide, or is corrosion resistant plate.Described titanium silicide nano line layer comprises at least a form in nano wire, nano-nail, nanometer rods, nano line cluster, the rocket shape nano wire.Described titanium silicide nano line layer is TiSi crystalline phase or TiSi
2Crystalline phase.Described amorphous silicon membrane layer is the film that chemical vapour deposition (CVD) or magnetron sputtering deposition become.
The invention has the beneficial effects as follows: with the titanium silicide nano line as derivant, on the one hand, titanium silicide and the crystal silicon mismatch degree on lattice constant is little than other metals, so easier amorphous silicon membrane crystallization of inducing, amorphous silicon has lower nucleating potential barrier in crystallization process, crystallization temperature is lower, drops to below 400 ℃; On the other hand, the specific area that the titanium silicide nano line is huge increases the contact area between inducing layer and the amorphous silicon, and the amorphous silicon crystallization starting stage, the forming core number increases, and crystalline rate is greatly improved, and whole crystallization process was at 2 to 4 hours.
Description of drawings
Fig. 1 is the cross section structure schematic diagram of polysilicon membrane of the present invention.
Number in the figure explanation: 1-substrate, 2-transition zone, 3-layer polysilicon film.
Embodiment
The present invention will be further described by embodiment below in conjunction with accompanying drawing.
As shown in Figure 1, polysilicon membrane of the present invention comprises substrate 1 and layer polysilicon film 3, has the transition zone 2 of the titanium silicide nano line that is combined with each other with the two and polysilicon membrane coexistence between substrate 1 and the layer polysilicon film 3.Further, substrate is the transparent conductive oxide film glass of tin oxide or zinc oxide, or is corrosion resistant plate.The titanium silicide nano line comprises at least a form in nano wire, nano-nail, nanometer rods, nano line cluster, the rocket shape nano wire.The titanium silicide nano line is TiSi crystalline phase or TiSi
2Crystalline phase.
Embodiment 1:
1) with tin oxide transparent conductive glass (F-SNO
2) be substrate 1, adopt chemical vapour deposition technique on substrate 1, to deposit one deck titanium silicide thin layer and titanium silicide nano line composite construction, the titanium silicide nano line comprises nano wire, nano-nail, nanometer rods, nano line cluster, is the TiSi crystalline phase;
2) the amorphous silicon membrane layer of the plasma activated chemical vapour deposition of adopting 13.56MHZ deposition one deck 1 μ m on titanium silicide film that step 1) makes and titanium silicide nano line composite construction;
3) with step 2) the amorphous silicon membrane layer that makes is in 400 ℃ of annealing heat treatment 1h down, makes the titanium silicide nano line induce the layer polysilicon film of amorphous silicon membrane layer crystallization becoming megacryst grain, finally obtains large grain size polysilicon film shown in Figure 1.
Embodiment 2:
1) be substrate with ZnO transparent conductive glass (Ag-ZnO), adopt chemical vapour deposition technique on substrate 1, to deposit one deck titanium silicide film and titanium silicide nano line composite construction, the titanium silicide nano line comprises nano wire, nano-nail, rocket shape nano wire, is the TiSi crystalline phase;
2) the amorphous silicon membrane layer of the plasma activated chemical vapour deposition of adopting 13.56MHZ deposition one deck 2 μ m on titanium silicide film that step 1) makes and titanium silicide nano line composite construction;
3) with step 2) the amorphous silicon membrane layer that makes is in 400 ℃ of annealing heat treatment 2h down, makes the titanium silicide nano line induce the layer polysilicon film of amorphous silicon membrane layer crystallization becoming megacryst grain, finally obtains large grain size polysilicon film shown in Figure 1.
Embodiment 3:
1) with tin oxide transparent conductive glass (F-SNO
2) be substrate, adopt solid reaction process on substrate 1, to prepare the titanium silicide nano line, the titanium silicide nano line comprises nano-nail, nanometer rods, nano line cluster, rocket shape nano wire, is TiSi
2Crystalline phase;
2) adopt magnetron sputtering method on the titanium silicide nano line that step 1) makes, to deposit the amorphous silicon membrane layer of 3 μ m;
3) with step 2) amorphous silicon membrane that makes is in 400 ℃ of annealing heat treatment 2h down, makes the titanium silicide nano line induce the layer polysilicon film of amorphous silicon membrane layer crystallization becoming megacryst grain, finally obtains large grain size polysilicon film shown in Figure 1.
Embodiment 4:
1) be substrate with ZnO transparent conductive glass (Ag-ZnO), adopt solid reaction process to prepare the titanium silicide nano line on substrate 1, the titanium silicide nano line comprises nano-nail, nanometer rods, nano line cluster, is TiSi
2Crystalline phase;
2) adopt magnetron sputtering method on the titanium silicide nano line that step 1) makes, to deposit the amorphous silicon membrane layer of 2 μ m;
3) with step 2) amorphous silicon membrane that makes is in 350 ℃ of annealing heat treatment 4h down, makes the titanium silicide nano line induce the layer polysilicon film of amorphous silicon membrane layer crystallization becoming megacryst grain, finally obtains large grain size polysilicon film shown in Figure 1.
Embodiment 5:
1) with the stainless steel is substrate, adopt chemical vapour deposition technique on substrate 1, to deposit one deck titanium silicide film and titanium silicide nano line composite construction, the titanium silicide nano line comprises nano wire, nano-nail, nanometer rods, nano line cluster, rocket shape nano wire, is the TiSi crystalline phase;
2) adopt the amorphous silicon membrane layer of magnetron sputtering method deposition 2 μ m on titanium silicide film that step 1) makes and titanium silicide nano line composite construction;
3) with step 2) amorphous silicon membrane that makes is in 330 ℃ of annealing heat treatment 4h down, makes the titanium silicide nano line induce the layer polysilicon film of amorphous silicon membrane layer crystallization becoming megacryst grain, finally obtains large grain size polysilicon film shown in Figure 1.
Embodiment 6:
1) with the stainless steel be substrate, adopt solid reaction process to prepare the titanium silicide nano line on substrate 1, the titanium silicide nano line is a nano wire, is the TiSi crystalline phase;
2) adopt magnetron sputtering method on the titanium silicide nano line that step 1) makes, to deposit the amorphous silicon membrane layer of 3 μ m;
3) with step 2) amorphous silicon membrane that makes is in 350 ℃ of annealing heat treatment 4h down, makes the titanium silicide nano line induce the layer polysilicon film of amorphous silicon membrane layer crystallization becoming megacryst grain, finally obtains large grain size polysilicon film shown in Figure 1.
Embodiment 7:
1) with tin oxide transparent conductive glass (F-SNO
2) be substrate, adopt chemical vapour deposition technique on substrate 1, to deposit one deck titanium silicide film and titanium silicide nano line composite construction, the titanium silicide nano line is a nano-nail, is TiSi
2Crystalline phase;
2) the amorphous silicon membrane layer of the plasma activated chemical vapour deposition of adopting 13.56MHZ deposition 2 μ m on titanium silicide film that step 1) makes and titanium silicide nano line composite construction;
3) with step 2) amorphous silicon membrane that makes is in 350 ℃ of annealing heat treatment 3h down, makes the titanium silicide nano line induce the layer polysilicon film of amorphous silicon membrane layer crystallization becoming megacryst grain, finally obtains large grain size polysilicon film shown in Figure 1.
Through test, the inventive method can be on the thick substrate of 3-4mm deposition or the thick titanium silicide nano line layer of preparation 4-12nm, deposit the thick amorphous silicon membrane layer of 1-3um again on titanium silicide nano line layer, the last heat treatment 1-4h that anneals in 330-400 ℃ temperature range all can reach the object of the invention.
Claims (9)
1. polysilicon membrane comprises substrate (1) and layer polysilicon film (3), it is characterized in that: the transition zone (2) that has the coexistence of the titanium silicide nano line that is combined with each other with the two and polysilicon membrane between described substrate (1) and the layer polysilicon film (3).
2. polysilicon membrane according to claim 1 is characterized in that: described substrate (1) is the transparent conductive oxide film glass of tin oxide or zinc oxide, or is corrosion resistant plate.
3. polysilicon membrane according to claim 1 is characterized in that: described titanium silicide nano line comprises at least a form in nano wire, nano-nail, nanometer rods, nano line cluster, the rocket shape nano wire.
4. polysilicon membrane according to claim 1 is characterized in that: described titanium silicide nano line is TiSi crystalline phase or TiSi
2Crystalline phase.
5. the method for preparing polysilicon membrane with the amorphous silicon low temperature induction, it is characterized in that: on substrate (1), deposit titanium silicide nano wire layer and amorphous silicon membrane layer from bottom to top successively, induce amorphous silicon membrane layer crystallization becoming layer polysilicon film (3) by described titanium silicide nano line layer.
6. according to claim 5ly prepare the method for polysilicon membrane with the amorphous silicon low temperature induction, it is characterized in that: described substrate (1) is the transparent conductive oxide film glass of tin oxide or zinc oxide, or is corrosion resistant plate.
7. according to claim 5ly prepare the method for polysilicon membrane with the amorphous silicon low temperature induction, it is characterized in that: described titanium silicide nano line layer comprises at least a form in nano wire, nano-nail, nanometer rods, nano line cluster, the rocket shape nano wire.
8. according to claim 5ly prepare the method for polysilicon membrane with the amorphous silicon low temperature induction, it is characterized in that: described titanium silicide nano line layer is TiSi crystalline phase or TiSi
2Crystalline phase.
9. according to claim 5ly prepare the method for polysilicon membrane with the amorphous silicon low temperature induction, it is characterized in that: described amorphous silicon membrane layer is the film that chemical vapour deposition (CVD) or magnetron sputtering deposition become.
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CN103594195A (en) * | 2013-10-28 | 2014-02-19 | 中国科学院长春光学精密机械与物理研究所 | Method for making flexible, transparent and conductive film made of metal nanowires |
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CN103594195A (en) * | 2013-10-28 | 2014-02-19 | 中国科学院长春光学精密机械与物理研究所 | Method for making flexible, transparent and conductive film made of metal nanowires |
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