CN1407603A - Crystal silicon film semiconductor device and its manufacture, and photoelectric device - Google Patents
Crystal silicon film semiconductor device and its manufacture, and photoelectric device Download PDFInfo
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Abstract
Crystalline silicon film semiconductor device, photoelectric device and manufacture of the former device is disclosed herewith. Transparent electrodes are arranged on a glass substrate with non-crystalline silicon layer on it. A nickle layer is used as metal catalyst to contact with the non-crystalline silicon layer. Next, P polycrystal silicon layer with orientation and high crystallinity in formed by heating the non-crystalline silicon layer. And i and N polycrystal silicon layers are orderly formed on it. By the above structure, high performance crystalline silicon film semiconductor device with high crystallinity and orientation is produced.
Description
Technical field
The present invention relates to crystal silicon film semiconductor device, the crystal silicon film photoelectric device, manufacture method with crystal silicon film semiconductor device, be particularly related to crystal silicon film semiconductor device, the crystal silicon film photoelectric device, with the manufacture method of crystal silicon film semiconductor device, wherein, form polysilicon membrane as seed crystal with amorphous silicon.
Background technology
In semiconductor device such as solar cell, be the high-quality crystalline silicon devices of 1 to 1 μ m in order to form thickness thereon on the glass substrate that conductive film layer is arranged, should have thereon on the glass substrate of conducting film directly to form the high-quality seed crystal.Form this seed crystal and will satisfy following requirement:
(5) high crystalline (high-crystallinity)
(6) crystal orientation;
(7) high yield;
(8) K cryogenic treatment of simple glass substrate is used in permission;
During solar cell was made, the manufacturing process that adopts was at different substrates such as formation polysilicon membrane on glass at present.By this manufacturing process, do not need silicon wafer substrate with large-area high-quality.Therefore, can obviously reduce production costs.But, in the manufacturing of high performance semiconductor device, should improve the quality of polysilicon membrane.So far, usually with making substrate by high temperature resistant materials such as quartz, this substrate can stand high-temperature deposition to be handled, to be formed with the silicon thin film of good crystallinity.But, in this manufacturing process, owing to use for example quartzy expensive substrate, thereby can not reduce cost.
In order to address this problem, K, people IEEE such as yamomoto " First World conference on Phorovoltaic Energy Conversion ", 1575-1578 has reported a kind of method in (1994).By this method, use laser annealing, make the amorphous silicon membrane fusing, and crystallization, form film at substrate surface, thus, make the polysilicon membrane of good crystallinity.The advantage of this method is, can suppress underlayer temperature and raise, and might use substrate at a low price.And, in order on glass substrate, directly to form polysilicon, on glass substrate, formed conducting film with plasma CVD (plasma vapour deposition) method.
The open NO.82997/1997 of Japan's special permission discloses the another kind of method that addresses the above problem.By this method, make recrystallized amorphous silicon with metallic catalyst, to form P
+Conductivity type or n
-Whole crystallizing layers of conductivity type, or form the P that comprises BSF (back surface field) layer
-Or n
-Whole crystallizing layers of conductivity type.
But conventional crystal silicon film semiconductor device and crystal silicon film photoelectric device when making recrystallized amorphous silicon on the glass substrate with laser annealing, can not be handled a large amount of substrates without difficulty.This just the problem of output capacity occurred.Particularly, when with the melting crystal method noncrystal membrane being changed into the uniform polysilicon layer of crystal grain diameter, used method comprises: form noncrystal membrane with plasma CVD method, remove the hydrogen that contains in the amorphous silicon membrane with heat treatment, afterwards, carry out laser annealing.Thereby, a lot of troubles are arranged in the product manufacturing, and need a large amount of time, cause production cost to strengthen.
On the other hand, in the manufacture method, directly form polysilicon with plasma CVD on substrates such as glass and have quality problems, for example the degree of crystallinity of the polysilicon of Sheng Chenging is low.In the Pn structure and Pin structure of common employing in solar cell, P
-Conductivity type, or n
-The conductivity type polysilicon membrane will be formed directly on the glass substrate that conducting film is arranged on its surface.But the polysilicon membrane that is formed directly on the glass substrate with plasma CVD method has the problem that degree of crystallinity is low and carrier lifetime is short.Particularly, the P-type polysilicon membrane that forms with plasma CVD has serious technical problems such as the extremely low and crystal orientation difference of degree of crystallinity.
And, the method that discloses among the open NO.82997/1997 of Japan special permission, this conductor knot place that constitutes at the silicon of different conduction-types has nickle silicide (alloy of silicon and nickel) to exist.And, even removed remaining nickle silicide with etch, still defective can appear.Therefore, in the compound increase at semiconductor junction place.This can cause Solar cell performance obviously to reduce.
Summary of the invention
The purpose of this invention is to provide crystal silicon film semiconductor device, the manufacture method of crystal silicon film photoelectric device and crystal silicon film semiconductor device.Can obtain the high-crystallinity of polysilicon, excellent crystal orientation, high-performance and high production rate are arranged.
By the 1st feature of the present invention, crystal silicon film semiconductor device comprises:
The substrate that conductive layer is arranged on conductive substrates or its surface;
The 1st polysilicon layer of crystal orientation, its formation method are to introduce the metallic catalyst element in the amorphous silicon layer that forms on conductive substrates or the conductive layer, perhaps, the metallic catalyst element contacts with the surface portion of amorphous silicon layer, and the heat treatment amorphous silicon layer, makes its crystallization; With
The 2nd polysilicon layer, it is made seed crystal with the 1st amorphous silicon layer and forms, and its conduction type is identical with the conduction type of the 1st polysilicon layer.
By this structure, the metallic catalyst element is introduced in the amorphous silicon layer that is located on the substrate, perhaps contacts with amorphous silicon layer, afterwards, heat-treats, and through the effect of metallic catalyst element, amorphous silicon layer is transformed into the 1st polysilicon layer of crystal orientation at low temperatures.When making seed crystal form the 2nd polysilicon layer on the 1st silicon surface with the 1st silicon layer, the 2nd polysilicon layer of generation has identical crystal orientation and high-crystallinity with the 1st polysilicon layer as substrate.Equally, make the 3rd polysilicon layer that substrate forms with the 2nd polysilicon layer high-crystallinity and crystal orientation are also arranged.As a result, can make high-crystallinity, good crystal orientation, the crystal silicon film semiconductor device of high-performance and high yield.And there is not silicide at the semiconductor junction place that forms with the silicon of other conduction type.Therefore, need not provide the step of removing silicide, the defective that does not have silicide to cause.
By the present invention's the 2nd feature, the crystal silicon film photoelectric device comprises:
The dielectric substrate that conductive layer is arranged on conductive substrates or its surface;
The 1st polysilicon layer of the 1st conduction type, its formation method are that the amorphous silicon layer that forms on conductive substrates or the conductive layer surface is introduced the metallic catalyst element.Perhaps, the metallic catalyst element contacts with the amorphous silicon layer surface portion, and heat treatment, makes the amorphous silicon layer crystallization;
The 2nd crystallizing silicon layer, it is made seed crystal with the 1st crystallizing silicon layer and forms, and the 2nd is identical with the conduction type of the 1st crystallizing silicon layer;
Establishing on the 2nd polysilicon layer is the 3rd polysilicon layer of i-type basically;
Be located at the 4th polysilicon layer of establishing on the 3rd polysilicon layer that the conduction type different with the 1st conduction type arranged; With
Be located at the electronic section on the 4th polysilicon layer.
By the 3rd feature of the present invention, the crystal silicon film photoelectric device comprises:
The dielectric substrate that electrode is arranged on its surface;
The 1st polysilicon layer of the 1st conduction type, its formation method is that the amorphous silicon layer that forms on the electrode of dielectric substrate is introduced the metallic catalyst element, perhaps, the metallic catalyst element contacts with the surface portion of amorphous silicon layer, and heat treatment makes its crystallization to amorphous silicon layer;
Make the 2nd polysilicon layer that seed crystal forms with the 1st polysilicon layer, it has identical conduction type with the 1st polysilicon;
Be located at the 3rd polysilicon layer on the 2nd polysilicon layer, it has 2nd conduction type different with the 1st conduction type; With
Be located at the electrode part on the 3rd polysilicon layer.
In the structure of the present invention the 2nd and the 3rd feature, the metallic catalyst element is introduced in the amorphous silicon layer that is located on the substrate, perhaps, the metallic catalyst element contacts with amorphous silicon layer, the heat treatment amorphous silicon layer, under the metallic catalyst element interaction, amorphous silicon layer is transformed into the 1st polysilicon layer of crystal orientation at low temperatures.When making seed crystal form the 2nd polysilicon layer on the 1st silicon layer with the 1st silicon layer, the 2nd polysilicon layer of generation has identical crystal orientation and high-crystallinity with the 1st polysilicon layer as substrate.Equally, make the polysilicon layer that substrate forms with the 2nd polysilicon layer high-crystallinity and crystal orientation are also arranged.Therefore, can make high-crystallinity, crystal orientation, the crystal silicon film photoelectric device of high-performance and good productivity ratio.
By the present invention's the 4th feature, the manufacture method of crystal silicon film semiconductor device may further comprise the steps:
Conductive substrates is provided, or the substrate of conductive layer is arranged on its surface, and in conductive substrates or substrate, form amorphous silicon membrane on the surface of conductive layer;
The metallic catalyst element is introduced the surface portion contact of amorphous silicon layer inclusive NAND crystal silicon layer, and the heat treatment amorphous silicon layer makes its crystallization, forms the 1st polysilicon layer of crystal orientation;
Make seed crystal with the 1st polysilicon layer, on the 1st polysilicon layer, form 2nd polysilicon layer identical with its conduction type; With
Form 3rd polysilicon layer that 2nd conduction type arranged different on the 2nd polysilicon layer with its conduction type;
By this manufacture method, form amorphous silicon membrane on the substrate surface, the metallic catalyst element is introduced in the amorphous silicon layer, and perhaps, the metallic catalyst element contacts with the surface portion of amorphous silicon layer, afterwards, the heat treatment amorphous silicon layer.This is crystalizing amorphous silicon layer at low temperatures just, forms the 1st polysilicon layer of crystal orientation.Make seed crystal with the 1st polysilicon layer, when forming the 2nd polysilicon layer on the 1st polysilicon layer, the 1st is identical with the conduction type of the 2nd polysilicon layer, and crystal orientation is identical.And the conduction type of the 3rd polysilicon layer that forms on the 2nd polysilicon layer is different with the conduction type of the 2nd polysilicon layer, constitutes the semiconductor device of Pn structure.Therefore, can make high-crystallinity, crystal orientation, high-performance and large-duty crystal silicon film semiconductor device.
Description of drawings
Below with reference to the invention of accompanying drawing more detailed description, wherein:
Cross-sectional schematic when Fig. 1 is half stage in making by the solar cell of the present invention the 1st embodiment;
Fig. 2 is the cross-sectional schematic of solar cell completion status shown in Figure 1;
Fig. 3 is the cross-sectional schematic during half stage in making by the solar cell of the present invention's the 2nd preferred embodiment;
Fig. 4 is the cross-sectional schematic of solar cell completion status shown in Figure 3;
Cross-sectional schematic when Fig. 5 is half stage in making by the solar cell of the present invention the 4th embodiment;
Fig. 6 is the solar cell cutaway view by the present invention's the 5th preferred embodiment;
Embodiment
The preferred embodiment of accompanying drawings invention now.
＜the 1 preferred embodiment 〉
Fig. 1 and 2 has represented the 1st preferred embodiment by crystal silicon film semiconductor device of the present invention (crystal silicon film photoelectric device, i.e. Pin-type solar cell).Here, Fig. 1 represents that the present invention the 1st embodiment makes the state in half stage.Fig. 2 represents the completion status of crystal silicon film semiconductor device shown in Figure 1.The semiconductor device of the preferred embodiment comprises: glass substrate, be located at glass substrate on one side the main transparency electrode made from tin oxide and be located at solar cell on the transparency electrode.
As shown in Figure 1, substrate comprises the thick transparency electrode 2 of 800nm on the first type surface that is located on the glass substrate.SnO
2As transparency electrode 2, the surface of transparency electrode 2 is provided with concave-convex, the concave-convex of not drawing among Fig. 1.Introduce H on the surface of transparency electrode 2
2, SiH
2(silane) and B
2H
6The mist that (diborane) formed, under the pressure of 0.5Torr, substrate is heated to 420 ℃, with plasma CVD (P-CVD) method, forms the amorphous silicon layer 3 of the impure thick 20nm of P type under the frequency of 60MHz.The thickness of amorphous silicon layer 3 is not more than 50nm, and is preferably as far as possible little.Its reason is that in the crystallization of metallic catalyst element, amorphous silicon layer 3 is as seed crystal.
Afterwards, utilize vacuum evaporation to form the thick nickel dam 4 of 1nm as the metallic catalyst element.Subsequently, in nitrogen atmosphere, at 450 to 700 ℃, specifically at 500 ℃ to 600 ℃, heat treatment makes the diffusion of metallic catalyst elemental nickel.Heat treatment is not limited to carry out in nitrogen atmosphere, and in a vacuum, in the hydrogen atmosphere, in argon gas atmosphere or the halide atmosphere, heat treatment all can obtain heat treatment phase crystallization effect together in nitrogen atmosphere.
And, divide two stages to heat-treat.At first, in hydrogen atmosphere,, make the hydrogen amount of introducing amorphous silicon layer 3 be not more than 1%, preferably be not more than 0.3% 400 ℃ of heating.Afterwards, 550 ℃ of heating, the result forms the P type polysilicon layer 3A of high crystal orientation; As shown in Figure 2.The crystal orientation of polysilicon layer 3A is (110).In the said method, at first, on glass substrate 1, form amorphous silicon layer 3, afterwards, introduce the metallic catalyst element.Perhaps, adopt on glass substrate 1 directly at first depositing metal catalyst layer, promptly nickel dam 4, afterwards, form amorphous silicon layer 3.
Except that nickel, iron, cobalt, platinum, copper, gold etc. all can be used as the metallic catalyst element.The method that can be used for forming metal catalyst layer comprises: form with the form of film in the method for metal catalyst layer and use plasma treatment, vacuum evaporation, spin coating etc.Form in the method for metal catalyst layer with line or island form, use vacuum evaporation, under this state, cover the not part of deposit with metal mask.
And the method for metallic catalyst being introduced rete comprises: for example ion injects and plasma doping.Because metal catalyst layer is used for catalytic action, therefore, the concentration of catalyst elements is extremely low.Usually, metal catalyst layer is that gross thickness is the sandwich construction of the two-layer of several dusts or 3 layers.But as long as can introduce catalyst metals, metal catalyst layer also can be a single layer structure, and metallic catalyst reacts when catalyst metals arrives the relative edge by wanting the superficial layer of crystallization, and then whole superficial layer is in crystalline state.When the seed crystal quality is inessential, under staying state in the superficial layer, catalyst metals carries out crystallization.
By above-mentioned heat treatment, the metallic catalyst Elements Diffusion is advanced in the amorphous silicon layer 3, and be deposited in away from around the amorphous silicon layer 3 and the part between the transparent electrode layer 2 on metal catalyst layer one side, promptly, the metallic catalyst migration of element has only the trace meter catalyst elements to stay among the polysilicon layer 3A to the outmost surface of P-type polysilicon layer 3A.Therefore, can form high-quality P type polysilicon layer 3A.During the degree of crystallinity difference, nickle atom is stayed in the silicon layer.But, because only accounting for the ratio of whole solar cell thickness of detector, the seed crystal part is no more than 2%, therefore, the nickle atom of staying in the rete does not have big influence to Solar cell performance.
Therefore, even when the thickness of the polysilicon layer 3A of nickeliferous seed crystal is not more than 5nm, also quality that can damaged device can be made the high-quality device, and wherein, the major part that produces electric energy is not nickeliferous.And, to the crystallizing layer at the very important semiconductor junction place of solar device the multilayer crystallizing layer of the different conduction-types that is in contact with one another, the damage that had not both had remaining metallic catalyst also not cause because of corrosion.Therefore, can form desirable semiconductor junction.
Afterwards, introduce B
2H
6, H
2And SiH
4Mist, under the condition that pressure and the underlayer temperature of 0.5Torr is 200 ℃, use 60MHz P-CVD, form the thick P-type polysilicon layer 5 of 40nm.Subsequently, introduce H
2And SiH
4, form i type polysilicon layer 6 with 60MHz P-CVD at 300 ℃ underlayer temperatures.In this case, the essential thickness that absorbing light is used is not less than 500nm at least, preferably 10 μ m.But, also can adopt the thick thickness that reaches 50 μ m.At that time, the hydrogen content in the rete can be according to condition from 0.5 to 8%.Since with the metallic catalyst crystallization as the silicon layer 3A of substrate on form polysilicon layer 5, therefore, the crystal orientation of polysilicon layer 5 is identical with the crystal orientation of silicon layer 3A,, is oriented to (110) that is.Compare with directly form silicon layer on substrates such as glass, degree of crystallinity is fabulous, and therefore, assembly is suitable for solar cell device.
And, on i type polysilicon layer 6 substrates, introduce H
2, SiH
4And PH
3(phosphine) under the underlayer temperature condition of the pressure of 0.3Torr and 200 ℃, with 13.56MHz P-CVD method, forms the thick n-type polysilicon layer 7 of 50nm.The optimum thickness of polysilicon layer 7 changes with degree of crystallinity.But suitable thickness range is 10nm to 100nm, preferably 30nm to 60nm.At last, form the thick aluminium film 8 of 1 μ m with vacuum evaporation and make backplate.
With the method for attachment of routine, the surface electrode of a plurality of devices independent on the substrate and backplate are connected in series, constitute 50 utmost points and connect, as the semiconductor device of the above-mentioned type.The resultant device characteristic is the output voltage sum of each parts as output voltage.
In the said structure, backing material for example comprises, pottery, quartz and sapphire.Although the aluminium film is as backplate, silver, molybdenum and other metal also can be used as backplate.
In the structure of the 1st preferred embodiment, use glass substrate, the light transmission glass substrate.Perhaps, also can replace glass substrate, the light transmission film surface with metal substrate.The example of this structure below will be described.
＜the 2 preferred embodiment 〉
Fig. 3 and 4 expressions are by the 2nd preferred embodiment of crystal silicon film semiconductor device of the present invention (Pin-type solar cell).What Fig. 3 represented is the state that has carried out half stage in the solar cell manufacturing, and what Fig. 4 represented is the completion status of solar cell.
On soft SUS substrate 9, form the SiO of 200nm
2, film 10 is made dielectric film.Afterwards, SiO
2Form the thick SUS film 11 of 500nm on the surface of film 10 as backplate.Afterwards, with the thick amorphous silicon layer that contains p type impurity 12 of silicon target sputter 10nm on SUS film 11.SiO
2Hydrogen content in the film 10 is not more than 0.1%.Amorphous silicon layer 12 surperficial spin coating nickel salt solutions, dry coating forms nickel film 13.
Subsequently, in the hydrogen atmosphere of 1Torr,, make amorphous silicon layer 12 crystallizations 550 ℃ of heat treatments 30 minutes.Thus, amorphous silicon layer 12 is transformed into P-type polysilicon layer 12A, sees Fig. 4.At that time, the nickel in the nickel dam 13 of SUS film 11 and the near interface precipitation of P-type polysilicon layer 12A is not stayed among the P type polysilicon layer 12A basically.And, because P type polysilicon layer 12A does not have hydrogen basically, therefore, can carry out crystallization treatment evenly.On the P type polysilicon layer 12A, introduce B
2H
6, H
2And SiH
4Mist, under the pressure of 0.5Torr and 200 ℃ of underlayer temperature conditions, with 60MHz P-CVD form 40nm thick be the polysilicon layer 14 of P type basically.Afterwards, introduce H
2And SiH
4Mist at 300 ℃ underlayer temperature, is used 60MHz P-CVD, form 2 μ m thick be the polysilicon layer 15 of i type basically.
And, introduce H
2And SiH
4And PH
3Mist under the pressure of 0.3Torr and the 300 ℃ of underlayer temperature conditions, is used 13.56MHz P-CVD, form 20nm thick be the polysilicon layer 16 of n type basically.Form thick ITD (tin indium oxide) film 17 of 70nm and make transparency electrode, form the thick aluminum metal electrode 18 of 1 μ m on the partially transparent electrode.Under this situation, every layer of polysilicon layer 14,15 and 16 crystal orientation are (110).Press the P-CVD condition, the crystal orientation of polysilicon layer 16 also can be (111).The polysilicon that with crystal orientation is (111) is compared, and crystal orientation is that the polysilicon of (110) has natural crystal structure surface.
＜the 1 Comparative Examples 〉
In the preparation polycrystalline silicon film solar cell device, general conventional method is to form whole polysilicon layers with the P-CVD method.Below will describe in detail with the present invention the 1st preferred embodiment has same structure, with polycrystalline silicon film solar cell contrast of the present invention, polycrystalline silicon film solar cell.
Specifically, introduce H
2And SiH
4And B
2H
6Mist, under the pressure of 0.5Torr and 200 ℃ of underlayer temperature conditions,, form the polysilicon layer of P type with 50MHz PCVD method.Introduce H
2And SiH
4Mist under the pressure of 0.5Torr and 300 ℃ of underlayer temperature conditions, with 60MHz P-CVD method, forms i type layer.Introduce H
2And SiH
4And PH
3Mist, under the pressure of 0.3Torr and 300 ℃ of underlayer temperature conditions,, form n type layer with 13.56MHz P-CVD method.
The current-voltage of the solar cell device that test forms like this.As a result, the characteristic curve duty factor FF of measurement solar cell properties changes.(Voc * Jc), Pmax is a peak power output to the FF=Pmax/ here in the formula, and Voc is a discharge voltage, and Jsc is a short-circuit photocurrent density.Specifically, by the duty factor FF of the polysilicon solar cell device of the 1st preferred embodiment be by the polysilicon solar cell of the 1st Comparative Examples can device 1.47 times of duty factor.Therefore, owing to use and to have used the P layer (polysilicon layer 12A) of metallic catalyst crystallization to make seed crystal, make the performance of polysilicon solar cell of the present invention's the 1st preferred embodiment better than the Solar cell performance of the 1st Comparative Examples that forms whole polysilicon layers with the P-CVD method.
＜the 2 Comparative Examples 〉
With the mode identical with the 1st Comparative Examples, use the P-CVD method, prepare the polysilicon solar cell that the 2nd Comparative Examples of identical structure is arranged with the present invention's the 2nd preferred embodiment.The polysilicon solar cell device of making is like this compared with the polysilicon solar cell device of the present invention's the 2nd preferred embodiment.As a result, by the duty factor FF of the polysilicon solar cell device of the present invention's the 2nd preferred embodiment be 1.44 times of duty factor of the polysilicon solar cell of the 2nd Comparative Examples.As the 1st preferred embodiment, in the 2nd preferred embodiment, with making seed crystal by the P layer of metallic catalyst crystallization, the performance of the solar cell device of making is better than the performance of the solar cell device made from conventional method.
＜the 3 preferred embodiment 〉
The 3rd preferred embodiment of the present invention below will be described.In the 1st and the 2nd preferred embodiment, amorphous silicon layer 3,12 has been introduced metallic catalyst and crystallization, and the crystal orientation of the crystallizing layer of generation is (110).On the other hand, in the 3rd preferred embodiment, form the thick amorphous silicon layer of 18nm that contains p type impurity on the transparency electrode 2 in the 1st preferred embodiment.Introduce H
2And SiH
4And B
2H
6Mist, be under the condition of (111) at crystal orientation, in VHF (extremely high frequency) scope, use the P-CVD method, on amorphous silicon layer, form the thick polysilicon layer of 2nm.Subsequently, using vacuum evaporation, is on the polysilicon layer of (111) at crystal orientation, forms the thick nickel dam of 2nm, afterwards, and 500 ℃ of heat treatments 1 hour.The crystal orientation of the polysilicon layer that has changed from amorphous silicon layer with heat treatment is (111).Form the Pin structure by the mode identical with the 1st preferred embodiment.As a result, all the crystal orientation of silicon layer is (111).Test is by the electrical property of the solar cell device of the 3rd preferred embodiment.Found that duty factor FF is 0.98 times by the duty factor of the solar cell of the present invention's the 1st preferred embodiment.
In these above-mentioned preferred embodiments, preparation has the solar cell device of Pin structure.But,, therefore, might make P-n type solar cell because the polysilicon of making by the inventive method has good performance.This P-n type solar cell will describe as the 4th preferred embodiment.
＜the 4 preferred embodiment 〉
Fig. 5 illustrates the present invention's the 4th preferred embodiment, and wherein, P-n type solar cell is as the crystal silicon film photoelectric device that is provided with on glass substrate.Specifically, shape or the thick SiO of 200nm on the glass substrate 27
2Film 19 is as insulating barrier.Also form the thick SUS film 20 of 500nm as backplate.Subsequently, sputter forms the thick amorphous silicon layer 21 that contains n type impurity of 10nm.Shown in Fig. 2 or 4, on amorphous silicon layer 21, form the thick Raney nickel layer (not having picture) of 2nm, afterwards, heat-treat at 500 ℃, amorphous silicon layer 21 is transformed into polysilicon layer 22A.22A makes seed crystal with this polysilicon layer, carries out VHF P-CVD, forms the thick n type polysilicon layer (not having picture) of 2 μ m.The resistance value of this n type polysilicon layer is 20 to 100 Ω cm.Also on n type polysilicon layer, form the thick P type polysilicon layer 23 of 500nm with VHF P-CVD.The resistance value of this P type polysilicon layer 23 is 0.1 to 30 Ω cm.Also form the thick ITO film 24 of 70nm on the P type polysilicon layer 23 and make transparency electrode.Form aluminium film 25 on the ITO film 24 and make electrode, form metal electrode 26 on the part aluminium film 25.
By the solar cell of the 4th preferred embodiment of the present invention, be 50 grades of solar cells that connect into by backplate and the surface electrode mode of being connected in series.As a result, the performance as the output voltage of battery is the output voltage sum of each parts.
Fig. 6 illustrates the present invention's the 5th preferred embodiment, and wherein, glass substrate is provided with Pin type solar cell as the silicon thin film photoelectric device.Specifically, form transparency electrode 29 on the glass substrate 28.SnO
2As transparency electrode 29.Form the nickel Catalytic Layer on the transparency electrode 29, afterwards, form the thick amorphous silicon layer that contains n type impurity of 20nm, afterwards, in nitrogen atmosphere, make the diffusion of nickel metal catalytic layer, make the amorphous silicon layer crystallization at 550 ℃.Subsequently, introduce H
2, SiH
4And B
2H
6Mist, at VHF district P-CVD, form the thick P type polysilicon layer 31 of 40nm.The crystal orientation of this polysilicon layer 31 is (111).Introduce H
2And SiH
4Mist, use VHF P-CVD, form the thick i type polysilicon layer 32 of 1 μ m.Afterwards, introduce PH
3, H
2And SiH
4Mist, use VHF P-CVD, form the thick n type polysilicon layer 33 of 50 μ m.Under certain conditions, the crystal orientation of i type layer and n type layer can be (110).At last, form the thick aluminium film 34 of 1 μ m with vacuum evaporation and make backplate.The crystalline texture on this polysilicon film surface is fit to do photoelectric device.And, because the P layer has high-crystallinity as substrate, the performance of this device is compared with P-CVD directly at SnO
2The device performance that forms the P layer is good.
＜the 3 Comparative Examples 〉
The structure of the solar cell device of the 3rd Comparative Examples only forms with P-CVD, and is identical with the structure of the solar cell device of pressing the present invention the 5th embodiment.The characteristic of the solar cell device of the 3rd Comparative Examples is compared with the performance of the solar cell device of the 5th preferred embodiment.As a result, the duty factor of the solar cell device of the 5th preferred embodiment is 1.51 times of duty factor of the 3rd Comparative Examples solar cell device.Therefore, the performance with the solar cell device of the 5th preferred embodiment of metallic catalyst crystallization is better than the performance of the solar cell device made from conventional method.
Above-mentioned when being used for solar cell, can be used in the various application, for example, be used in the civilian power supply, in addition, can be used in the portable set, as electronic calculator and wrist-watch by crystal silicon film semiconductor device of the present invention and crystal silicon film photoelectric device.
As mentioned above, comprise by crystal silicon semiconductor device of the present invention: the 1st polysilicon layer, its formation method is, introduce the metallic catalyst element in the amorphous silicon layer on the substrate, perhaps, the metallic catalyst element contacts with amorphous silicon layer, and heat treatment makes it become the polysilicon layer of crystal orientation at low temperatures through the metallic catalyst role transformation to amorphous silicon layer afterwards; The 2nd polysilicon layer is to make seed crystal with the 1st polysilicon layer to form, and therefore, it has high-crystallinity and identical crystal orientation as the 1st polysilicon layer; With the 3rd polysilicon layer, it is made substrate with the 2nd polysilicon layer and forms.Because this structure is arranged, crystal silicon film semiconductor device has high-crystallinity, crystal orientation, high production rate and good performance.Particularly, on low-cost substrate, for example on glass substrate, form thin-film solar cells easily, and, can produce the high-performance crystal silicon film semiconductor device at low cost.And, owing to do not have silicide at semiconductor junction place with other conduction type, thereby the defective that does not exist silicide to cause.
Comprise by crystal silicon film photoelectric device of the present invention: the 1st polysilicon layer, its formation method is, the metallic catalyst element is introduced in the amorphous silicon layer that is provided with on the substrate, perhaps, the metallic catalyst element contacts with amorphous silicon, afterwards, and the heat treatment amorphous silicon layer, through the metallic catalyst element interaction, make amorphous silicon be transformed into the polysilicon layer of crystal orientation; The 2nd polysilicon layer is made seed crystal with the 1st polysilicon layer and is formed on the 1st polysilicon layer, and it has crystal orientation and the high-crystallinity identical with the 1st polysilicon layer; With the 3rd polysilicon layer that high-crystallinity and crystal orientation are arranged that is located on the 2nd polysilicon layer.Because this structure is arranged, the crystal silicon film photoelectric device has high-crystallinity, good crystal orientation, good performance and high productivity ratio.
Manufacture method by crystal silicon film semiconductor device of the present invention may further comprise the steps: form amorphous silicon film on the substrate surface; The metallic catalyst element is introduced in the amorphous silicon layer, perhaps contacts with the surface portion of amorphous silicon layer, and the heat treatment amorphous silicon layer makes its crystallization at low temperatures, forms the 1st polysilicon layer of crystal orientation; Make seed crystal forms identical conduction type and crystal orientation with it the 2nd polysilicon layer thereon with the 1st polysilicon layer; Form 3rd polysilicon layer different on the 2nd polysilicon layer with its conduction type.Use this structure, can make high-crystallinity, crystal orientation, premium properties and large-duty crystal silicon film semiconductor device are arranged.When particularly invention is used for thin-film solar cells, can use for example low-cost substrate of glass substrate, thereby can low-cost production go out high performance semiconductor device.
Describe invention in detail referring to preferred embodiment, but should be appreciated that, in the invention scope that appended claims limits, also have various changes and modifications.
Claims (16)
1, crystal silicon film semiconductor device comprises:
The substrate that conductive layer is arranged on conductive substrates or its surface;
The 1st polysilicon layer of crystal orientation, its formation method is that the metallic catalyst element is introduced the amorphous silicon layer that forms on conductive substrates or the conductive layer surface, perhaps, the metallic catalyst element contacts with the surface portion of amorphous silicon layer, and the heat treatment amorphous silicon layer makes its crystallization; With
That does with the 1st polysilicon layer that seed crystal forms has the 2nd polysilicon layer of identical conduction type with the 1st polysilicon layer.
2, by the crystal silicon film semiconductor device of claim 1, wherein, the hydrogen content in the 2nd polysilicon layer is not less than 0.1%.
3, by the crystalline membrane semiconductor device of claim 1, wherein, the 2nd polysilicon layer is pressed the thickness direction crystalline orientation.
4, by the crystal silicon film semiconductor device of claim 1, wherein, the 1st is identical with the crystalline orientation of the 2nd polysilicon layer.
5, by the crystal silicon film semiconductor device of claim 1, its also comprise be located in the 2nd polysilicon layer away from 3rd polysilicon layer of the 1st polysilicon layer on one side, the 3rd polysilicon layer has 2nd conduction type different with the conduction type of the 2nd polysilicon layer.
6, by the crystal silicon film semiconductor device of claim 5, comprise that also be located at the 4th polysilicon layer between the 3rd and the 2nd polysilicon layer, the 4th polysilicon layer has 3rd conduction type different with the conduction type of the 2nd and the 3rd polysilicon layer.
7, by the crystal silicon film semiconductor device of claim 5, wherein, the 3rd has identical crystal orientation with the 2nd polysilicon layer.
8, by the crystal silicon film semiconductor device of claim 6, wherein, the 4th has identical crystalline orientation with the 2nd polysilicon layer.
9, by claim 6 or 8 crystal silicon film semiconductor device, wherein, the 4th has identical crystalline orientation with the 3rd polysilicon layer.
10, by the crystal silicon film semiconductor device of claim 5 or 6, wherein, the hydrogen content in the 3rd and the 4th polysilicon layer is not less than 0.1%.
11, crystal silicon film photoelectric device comprises:
The dielectric substrate that conductive layer is arranged on conductive substrates or its surface;
The 1st polysilicon layer of the 1st conduction type, its formation method is that the metallic catalyst element is introduced the amorphous silicon layer that forms on conductive substrates or the conductive layer surface, perhaps, the metallic catalyst element contacts with the surface portion of amorphous silicon layer, and the heat treatment amorphous silicon layer makes its crystallization;
That does with the 1st polysilicon layer that seed crystal forms has the 2nd polysilicon layer of identical conduction type with the 1st polysilicon layer;
Be located on the 2nd polysilicon layer is the 3rd polysilicon layer of i type basically;
Be located at having on the 3rd polysilicon layer and be different from the 4th polysilicon layer of the 2nd conduction type of the 1st conduction type; With
Be located at the electrode part on the 4th polysilicon layer.
12, by the crystal silicon film photoelectric device of claim 11, wherein, conductive substrates is a stainless steel substrates; With the substrate that conductive layer is arranged on its surface be glass.
13, crystal silicon film photoelectric device comprises:
The dielectric substrate that electrode is arranged on its surface;
The 1st polysilicon layer of the 1st conduction type, its formation method be, the metallic catalyst element is introduced the amorphous silicon layer that forms on the electrode of dielectric substrate, and perhaps, the metallic catalyst element contacts with the surface portion of amorphous silicon layer, and the heat treatment amorphous silicon layer makes its crystallization;
That does with the 1st polysilicon layer that seed crystal forms has the 2nd polysilicon layer of identical conduction type with the 1st polysilicon layer;
Be located at the 3rd polysilicon layer that 2nd conduction type different with the 1st conduction type arranged on the 2nd polysilicon layer; With
Be located at the electrode part on the 3rd polysilicon layer.
14, the manufacture method of crystal silicon film semiconductor device may further comprise the steps:
The substrate that conductive layer is arranged on conductive substrates or its surface is set, forms amorphous silicon membrane on the conductive layer surface in conductive substrates or the substrate;
The metallic catalyst element is introduced the surface portion contact of amorphous silicon layer inclusive NAND crystal silicon layer, and the heat treatment amorphous silicon layer makes its crystallization, forms the 1st polysilicon layer of crystal orientation;
Make seed crystal with the 1st polysilicon layer and form 2nd polysilicon layer identical thereon with its conduction type; With
Form the 3rd polysilicon layer on the 2nd polysilicon layer, the 3rd polysilicon layer has 2nd conduction type different with the conduction type of the 2nd polysilicon layer.
15, by the method for claim 14, wherein, the hydrogen content in the amorphous silicon layer is not more than 0.3%.
16, by the method for claim 14 or 15, wherein, the thickness of amorphous silicon layer is not more than 50nm.
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| CN01140772A CN1407603A (en) | 2001-08-25 | 2001-08-25 | Crystal silicon film semiconductor device and its manufacture, and photoelectric device |
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| CN01140772A CN1407603A (en) | 2001-08-25 | 2001-08-25 | Crystal silicon film semiconductor device and its manufacture, and photoelectric device |
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| CN1407603A true CN1407603A (en) | 2003-04-02 |
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| CN01140772A Pending CN1407603A (en) | 2001-08-25 | 2001-08-25 | Crystal silicon film semiconductor device and its manufacture, and photoelectric device |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100337304C (en) * | 2003-08-22 | 2007-09-12 | 友达光电股份有限公司 | Method for forming polycrystalline silicon layer |
| CN100349259C (en) * | 2003-04-07 | 2007-11-14 | 友达光电股份有限公司 | Method for making low-temp. polycrstalline silicon film |
| US7374979B2 (en) | 2004-08-13 | 2008-05-20 | Samsung Sdi Co., Ltd. | Thin film transistor and method of fabricating the same |
| CN1975989B (en) * | 2005-12-01 | 2010-09-29 | 香港科技大学 | Polycrystalline silicon film preparation method, polycrystalline silicon and film transistor prepared therefor |
| CN103178149A (en) * | 2011-12-21 | 2013-06-26 | 松下电器产业株式会社 | Thin film solar cell and method for manufacturing same |
| CN108963013A (en) * | 2017-05-19 | 2018-12-07 | Lg电子株式会社 | Solar battery and its manufacturing method |
| CN109935658A (en) * | 2017-12-18 | 2019-06-25 | 株式会社爱发科 | The manufacturing method of solar battery |
| CN113454755A (en) * | 2019-02-19 | 2021-09-28 | 应用材料公司 | Polysilicon liner |
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2001
- 2001-08-25 CN CN01140772A patent/CN1407603A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100349259C (en) * | 2003-04-07 | 2007-11-14 | 友达光电股份有限公司 | Method for making low-temp. polycrstalline silicon film |
| CN100337304C (en) * | 2003-08-22 | 2007-09-12 | 友达光电股份有限公司 | Method for forming polycrystalline silicon layer |
| US7374979B2 (en) | 2004-08-13 | 2008-05-20 | Samsung Sdi Co., Ltd. | Thin film transistor and method of fabricating the same |
| US7423322B2 (en) | 2004-08-13 | 2008-09-09 | Samsung Sdi Co., Ltd. | Thin film transistor and method of fabricating the same |
| CN1975989B (en) * | 2005-12-01 | 2010-09-29 | 香港科技大学 | Polycrystalline silicon film preparation method, polycrystalline silicon and film transistor prepared therefor |
| CN103178149A (en) * | 2011-12-21 | 2013-06-26 | 松下电器产业株式会社 | Thin film solar cell and method for manufacturing same |
| CN103178149B (en) * | 2011-12-21 | 2016-08-24 | 松下知识产权经营株式会社 | Thin film solar cell and method for manufacturing same |
| CN108963013A (en) * | 2017-05-19 | 2018-12-07 | Lg电子株式会社 | Solar battery and its manufacturing method |
| CN108963013B (en) * | 2017-05-19 | 2022-05-27 | Lg电子株式会社 | Solar cell and method for manufacturing same |
| CN109935658A (en) * | 2017-12-18 | 2019-06-25 | 株式会社爱发科 | The manufacturing method of solar battery |
| CN113454755A (en) * | 2019-02-19 | 2021-09-28 | 应用材料公司 | Polysilicon liner |
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