CN114843175A - N-type doped oxide microcrystalline silicon, heterojunction solar cell and preparation methods of N-type doped oxide microcrystalline silicon and heterojunction solar cell - Google Patents

N-type doped oxide microcrystalline silicon, heterojunction solar cell and preparation methods of N-type doped oxide microcrystalline silicon and heterojunction solar cell Download PDF

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CN114843175A
CN114843175A CN202210480356.4A CN202210480356A CN114843175A CN 114843175 A CN114843175 A CN 114843175A CN 202210480356 A CN202210480356 A CN 202210480356A CN 114843175 A CN114843175 A CN 114843175A
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Abstract

The invention discloses an N-type doped oxide microcrystalline silicon, a heterojunction solar cell and preparation methods of the N-type doped oxide microcrystalline silicon and the heterojunction solar cell, and belongs to the technical field of solar cells. Mixing silane, hydrogen, an N-type doping source gas and nitrous oxide for CVD reaction, and depositing to obtain N-type doping oxidation microcrystalline silicon; the N-type doping source gas comprises Va group and/or VIA group elements. The invention can effectively improve the utilization rate of incident light, and can improve the conductivity of the N-type doped microcrystalline silicon oxide by improving the crystallinity of the N-type doped microcrystalline silicon oxide, thereby improving the conversion efficiency of the solar cell.

Description

N-type doped oxide microcrystalline silicon, heterojunction solar cell and preparation methods of N-type doped oxide microcrystalline silicon and heterojunction solar cell
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to an N-type doped oxidized microcrystalline silicon, a heterojunction solar cell and preparation methods of the N-type doped oxidized microcrystalline silicon and the heterojunction solar cell.
Background
For the existing HJT heterojunction solar cell, the N-type doped layer is usually prepared by adopting a microcrystalline oxide process, and the microcrystalline N-type oxide process has the advantage that an amorphous N layer with high incident light absorption can be changed into a microcrystalline N oxide layer with low absorption coefficient. Whereas existing techniques for oxidizing microcrystals use carbon dioxide (CO) 2 ) The oxygen source is doped, the purpose of adding carbon dioxide is to increase the doping oxygen source of the oxidized microcrystalline film, one purpose of the doping oxygen source is to enable the refractive index of the film layer to be adjustable (the refractive index N is 1.8-3.7) so as to achieve a better light reflection resistance effect, and the other purpose is to enable the microcrystalline N oxide layer added with oxygen to greatly reduce the absorption coefficient of the film compared with the oxygen-free microcrystalline N layer, so that the battery efficiency is improved.
However, the problems of the N-type oxide microcrystals are that: the existing oxygen doping gas is carbon dioxide, and the addition of an oxygen source in the carbon dioxide influences the crystallinity (Raman measurement) of the microcrystalline N film, so that the crystallinity of the film is lowered, and the lower crystallinity directly increases the resistivity of the film. The applicant has found that to avoid an excessive increase in resistance, it is necessary to dope the carbon dioxide (CO) ratio 2 /SiH 4 ) The doping ratio of carbon dioxide is controlled to be between 0.5 and 2, but even in this case, the refractive index interval (n is 2.3 to 2.9) of optical anti-reflection is not easily satisfied at the same time, and the conversion efficiency of the battery is reduced.
Therefore, there is a need to develop a new doped oxygen source to overcome the shortcomings of the prior art to solve or alleviate the above problems.
Disclosure of Invention
1. Problems to be solved
Aiming at the problem that the existing oxide microcrystal technology of an N-type semiconductor is difficult to meet the requirements of film resistivity and cell conversion efficiency at the same time, the invention provides an N-type doped oxide microcrystal silicon, a heterojunction solar cell and preparation methods of the N-type doped oxide microcrystal silicon and the heterojunction solar cell; the problems are effectively solved by changing the doping oxygen source and improving the doping process.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to a preparation method of N-type doped oxidation microcrystalline silicon, which is used for a solar cell and comprises the steps of mixing silane, hydrogen, an N-type doped source gas and nitrous oxide for CVD reaction, and depositing to obtain the N-type doped oxidation microcrystalline silicon; the N-type doping source gas comprises Va group and/or VIA group elements.
For an N-type dopant source gas, the effect is to dope free electrons into the silicon such that the free electron concentration in the film is greater than the hole concentration. The outermost layer of group va and/or group via elements has more electrons than the outermost layer of group via elements, and doping the hydride can satisfy the requirement of N-type doping.
Preferably, the volume ratio of nitrous oxide to silane is between 10% and 60%.
Preferably, the volume ratio of nitrous oxide to silane is between 10% and 30%.
Preferably, the specific steps are as follows:
(1) putting the silicon substrate into a cavity of CVD equipment, and vacuumizing the CVD equipment;
(2) introducing silane, hydrogen, an N-type doping source gas and nitrous oxide into a vacuum cavity of the CVD equipment according to the preset reaction gas dosage;
(3) and (3) starting a power supply of the CVD equipment to dissociate the gas in the step (2) to form plasma type atoms, and depositing the plasma type atoms on the silicon substrate after the plasma type atoms are combined to obtain the N-type doped microcrystalline silicon oxide.
Preferably, in the step (2), the silane is used in an amount of 50sccm to 300sccm, the hydrogen is used in an amount of 3000sccm to 30000sccm, the nitrous oxide is used in an amount of 10sccm to 150sccm, and the N-type dopant source gas includes the phosphane in an amount of 250sccm to 1500 sccm.
Preferably, in the step (3), the output power of the power supply is not lower than 1000W, and the deposition time is 1 min-5 min.
The N-type doped oxide microcrystalline silicon is prepared by the preparation method of the N-type doped oxide microcrystalline silicon.
The invention relates to a heterojunction solar cell, which comprises a first silicon layer and a second silicon layer; the first silicon layer is the N-type doped microcrystalline silicon oxide, the second silicon layer comprises crystalline silicon or amorphous silicon layer or microcrystalline silicon with the doping amount or doping type different from that of the first silicon layer, and the first silicon layer is arranged on the second silicon layer and has a space charge region between the first silicon layer and the second silicon layer.
Preferably, the solar cell sequentially comprises a back electrode, a TCO thin film, a P-type doped microcrystalline silicon thin film, an intrinsic amorphous silicon thin film, an N-type monocrystalline silicon, an intrinsic amorphous silicon thin film, the N-type doped microcrystalline silicon oxide, the TCO thin film and a front electrode which are connected in the thickness direction.
The invention relates to a preparation method of a heterojunction solar cell, wherein the heterojunction solar cell is the heterojunction solar cell provided by the invention, and the preparation method comprises the following specific steps:
(1) depositing intrinsic amorphous silicon thin films on two sides of the N-type monocrystalline silicon by a PECVD method;
(2) depositing the N-type doped microcrystalline silicon oxide on the intrinsic amorphous silicon thin film on the front side of the N-type monocrystalline silicon by a PECVD method, and depositing a P-type doped microcrystalline silicon thin film on the intrinsic amorphous silicon thin film on the back side of the N-type monocrystalline silicon;
(3) depositing TCO thin films on two sides of the thin film obtained in the step (2) by a PVD method;
(4) and finally, printing silver electrodes on two sides of the thin film obtained in the step (3) by a screen printing method to obtain the heterojunction solar cell.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the preparation method of the N-type doped microcrystalline silicon, in the process of preparing the N-type silicon by CVD, the nitrous oxide is doped to replace carbon dioxide in the prior art, so that an oxygen doping source can more effectively enter the N-type doped microcrystalline silicon film to participate in reaction, the light refractive index of the N-type doped microcrystalline silicon is effectively reduced, and the incident light utilization rate can be effectively improved when the N-type doped microcrystalline silicon is used for the incident light surface of a solar cell; meanwhile, the conductivity of the microcrystalline silicon can be improved by improving the crystallinity of the microcrystalline silicon, so that the conversion efficiency of the solar cell is improved.
(2) According to the preparation method of the heterojunction solar cell, the N-type doped microcrystalline silicon oxide effectively improves the current and the filling factor of the cell, and further improves the conversion efficiency of the cell.
Drawings
FIG. 1 is a schematic view of a heterojunction solar cell of the present invention;
FIG. 2 is a series resistance test chart of a heterojunction solar cell including an N-type doped microcrystalline silicon oxide thin film of comparative example 6;
FIG. 3 is a Raman spectrum at position J1 in FIG. 2 and corresponding crystallinity values;
FIG. 4 is a Raman spectrum at position J10 in FIG. 2 and the corresponding crystallinity values;
FIG. 5 is a Raman spectrum at position F5 in FIG. 2 and corresponding crystallinity values;
FIG. 6 is a Raman spectrum at position A1 in FIG. 2 and corresponding crystallinity values;
FIG. 7 is a Raman spectrum at position A10 in FIG. 2 and corresponding crystallinity values;
FIG. 8 is a series resistance test chart of a heterojunction solar cell including the N-type doped microcrystalline silicon oxide thin film of example 9;
FIG. 9 is a Raman spectrum at position J1 in FIG. 8 and its corresponding crystallinity values;
FIG. 10 is a Raman spectrum at position J10 in FIG. 8 and its corresponding crystallinity values;
FIG. 11 is a Raman spectrum at position E6 in FIG. 8 and its corresponding crystallinity values;
FIG. 12 is a Raman spectrum at position A1 in FIG. 8 and its corresponding crystallinity values;
fig. 13 is a raman spectrum at position a10 in fig. 8 and its corresponding crystallinity value.
In the figure:
1. an N-type single crystal silicon substrate; 2. an intrinsic amorphous silicon thin film; 3. an N-type doped oxide microcrystalline silicon film; 4. a P-type doped microcrystalline silicon thin film; 5. a transparent conductive film; 6. and an electrode.
Detailed Description
The following detailed description of exemplary embodiments of the invention refers to the accompanying drawings, which form a part hereof, and in which are shown by way of illustration exemplary embodiments in which the invention may be practiced, and in which features of the invention are identified by reference numerals. The following more detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is presented for purposes of illustration only and not limitation to describe the features and characteristics of the invention, to set forth the best mode of carrying out the invention, and to sufficiently enable one skilled in the art to practice the invention. It will, however, be understood that various modifications and changes may be made without departing from the scope of the invention as defined in the appended claims. The detailed description and drawings are to be regarded as illustrative rather than restrictive, and any such modifications and variations are intended to be included within the scope of the present invention as described herein. Furthermore, the background is intended to be illustrative of the state of the art as developed and the meaning of the present technology and is not intended to limit the scope of the invention or the application and field of application of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs; the terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention; as used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
It will be understood that when an element is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present; when an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present; the terms "first," "second," and the like as used herein are for illustrative purposes only.
The invention is further described with reference to specific examples.
Example 1
In this embodiment, as shown in fig. 1, the layer structure of the heterojunction solar cell sequentially includes TCO-P-I-N-TCO, where the P layer is a P-type doped layer, the I layer is an intrinsic silicon passivation layer, the N layer is an N-type doped layer, the TCO is a transparent conductive thin film layer, such as an indium tin oxide conductive thin film layer, and the TCO is provided with a silver electrode for collecting current. The specific preparation method of the heterojunction solar cell comprises the following steps:
(1) placing the cleaned and textured N-type monocrystalline silicon substrate 1 on a bearing support plate, placing the support plate in a cavity of PECVD equipment, and vacuumizing the PECVD equipment;
(2) introducing silane and hydrogen into a vacuum-pumping cavity, and depositing intrinsic amorphous silicon thin films 2 on two surfaces of an N-type monocrystalline silicon substrate 1 by PECVD;
(3) after the intrinsic amorphous silicon thin film 2 is deposited, introducing silane with the dosage of 100sccm, hydrogen with the dosage of 30000sccm, nitrous oxide with the dosage of 20sccm and phosphane with the dosage of 500sccm into a vacuumized cavity, starting a power supply, setting the output power of the power supply to be 3000W, performing enhanced chemical vapor deposition for 3min, and preparing an N-type doped oxidation microcrystalline silicon thin film 3 on the intrinsic amorphous silicon thin film on the front surface of the N-type monocrystalline silicon;
(4) after the N-type doped oxide microcrystalline silicon thin film 3 is prepared, taking the carrier plate out to the atmospheric environment, automatically turning the silicon wafer to the other side, putting the carrier plate into a cavity of PECVD equipment, vacuumizing the PECVD equipment, and depositing a P-type doped microcrystalline silicon thin film 4 on the intrinsic amorphous silicon thin film on the back side of the N-type monocrystalline silicon by a PECVD method;
(5) depositing transparent conductive films 5 mainly comprising ITO or AZO on two sides of the film obtained in the step (4) by a PVD (physical vapor deposition) or RPD (reactive vapor deposition) method;
(6) and finally, printing electrodes 6 containing silver or copper on two sides of the film obtained in the step (5) by a screen printing method or an electroplating method to obtain the heterojunction solar cell.
The embodiment also provides the N-type doped microcrystalline silicon oxide thin film 3 prepared in the step (3), and the refractive index N and the resistivity of the thin film are tested, the crystallization rate of the cell is tested, and the test results are recorded in table 1. When the crystallinity of the microcrystal is judged, the response of the crystal lattice is measured by using Raman, and the crystallinity of the film can be judged by the response value at a certain wavelength.
TABLE 1 comparison of the Properties of N-type doped microcrystalline silicon oxide films of the respective embodiments
Figure BDA0003627454100000051
Example 2
The present embodiment provides an N-type doped oxidized microcrystalline silicon thin film 3 and a heterojunction solar cell, which have substantially the same structures and preparation methods as those of embodiment 1, and mainly have the following differences:
1) the amount of nitrous oxide used was 20 sccm.
The refractive index N test and the resistivity test of the prepared N-type doped microcrystalline silicon oxide film 3, and the results of the crystallization rate test of the cell are recorded in table 1.
Example 3
The present embodiment provides an N-type doped oxidized microcrystalline silicon thin film 3 and a heterojunction solar cell, which have substantially the same structures and preparation methods as those of embodiment 1, and mainly have the following differences:
1) the amount of nitrous oxide used was 30 sccm.
The refractive index N test and the resistivity test of the prepared N-type doped microcrystalline silicon oxide film 3, and the results of the crystallization rate test of the cell are recorded in table 1.
Example 4
The present embodiment provides an N-type doped oxidized microcrystalline silicon thin film 3 and a heterojunction solar cell, which have substantially the same structures and preparation methods as those of embodiment 1, and mainly have the following differences:
1) the amount of nitrous oxide used was 60 sccm.
The refractive index N test and the resistivity test of the prepared N-type doped microcrystalline silicon oxide film 3, and the results of the crystallization rate test of the cell are recorded in table 1.
Example 5
The present embodiment provides an N-type doped oxidized microcrystalline silicon thin film 3 and a heterojunction solar cell, which have substantially the same structures and preparation methods as those of embodiment 2, and mainly have the following differences:
1) the amount of hydrogen used was 20000 sccm.
The refractive index N and the resistivity of the prepared N-type doped microcrystalline silicon oxide thin film 3 are tested, and the result of testing the crystallization rate of the cell is recorded in table 1.
Example 6
The present embodiment provides an N-type doped oxidized microcrystalline silicon thin film 3 and a heterojunction solar cell, which have substantially the same structures and preparation methods as those of embodiment 5, and mainly have the following differences:
1) the power supply output power is reduced to 2500W.
The refractive index N test and the resistivity test of the prepared N-type doped microcrystalline silicon oxide film 3, and the results of the crystallization rate test of the cell are recorded in table 1.
Example 7
The present embodiment provides an N-type doped oxidized microcrystalline silicon thin film 3 and a heterojunction solar cell, which have substantially the same structures and preparation methods as those of embodiment 6, and mainly have the following differences:
1) the amount of hydrogen was 15000 sccm.
The refractive index N test and the resistivity test of the prepared N-type doped microcrystalline silicon oxide film 3, and the results of the crystallization rate test of the cell are recorded in table 1.
Example 8
The present embodiment provides an N-type doped oxidized microcrystalline silicon thin film 3 and a heterojunction solar cell, which have substantially the same structures and preparation methods as those of embodiment 7, and mainly have the following differences:
1) the using amount of the nitrous oxide is 30 sccm;
2) the power supply output power is reduced to 2900W.
The refractive index N test and the resistivity test of the prepared N-type doped microcrystalline silicon oxide film 3, and the results of the crystallization rate test of the cell are recorded in table 1.
To demonstrate the advantages of the present invention using nitrous oxide as the oxygen doping source, the present invention has also previously conducted related experiments with carbon dioxide. When carbon dioxide is doped into the oxidized microcrystal N layer as doping gas, the refractive index and the resistivity of the film are higher due to the fact that the carbon dioxide is not easy to dissociate and the carbon dioxide is not easy to dope into the microcrystal N layer, in order to solve the problem, a large amount of input power of hydrogen and enhanced chemical vapor deposition (PECVD) of a manufacturing process needs to be increased to meet the requirements of dissociation and the refractive index, the hydrogen consumption of the oxidized microcrystal N layer is thousands of sccm to 1 ten thousands of sccm in the conventional small cavity PECVD, but the hydrogen consumption of a mass production machine is tens of thousands of even 10 tens of thousands of hydrogen, and the hydrogen consumption exceeds the pumping speed working range which can be borne by the conventional commercial vacuum pump.
The invention takes the relevant experiments of carbon dioxide as comparative examples, which are as follows:
comparative example
As shown in fig. 1, an intrinsic amorphous silicon thin film 2, a front N-type doped microcrystalline silicon thin film 3, a back P-type doped microcrystalline silicon thin film 4, a transparent conductive thin film 5 are sequentially formed on an N-type single crystal silicon substrate 1 by a PECVD process, and then an Ag electrode 6 is printed by a screen printing process.
Wherein the N-type doped microcrystalline silicon film on the front surface is deposited by enhanced chemical vapor deposition (PECVD), and the introduced gas is Silane (SiH) 4 ) Hydrogen (H) 2 ) Phosphane (PH) 3 ) And carbon dioxide (CO) 2 ) Referring to table 1, the gas is dissociated by PECVD to form plasma-type atoms, and the plasma-type atoms are bonded and deposited on the N-type single crystal silicon substrate coated with the intrinsic amorphous silicon thin film. Experiments of 5 comparative examples were conducted according to the difference in doping amount and the difference in power, and it can be seen from Table 1 that the ratio of carbon dioxide doping is strongly correlated with the refractive index of the N-type doped microcrystalline silicon thin film with CO 2 /SiH 4 The refractive index is greatly reduced by increasing the (%), but the resistivity of the synchronous N-type doped microcrystalline silicon film is greatly increased.
Therefore, as can be seen from comparison between the examples of the present invention and the comparative examples, when carbon dioxide in the N-type doped microcrystalline silicon thin film was replaced with nitrous oxide (N) 2 O), a lower resistivity film can be obtained at a film refractive index close to that of carbon dioxide, mainly due to nitrous oxide (N) 2 O) has better dissociation rate, and the oxygen source in the N-type doped microcrystalline silicon film can more effectively enter the N-type doped microcrystalline silicon film to participate in the reaction. According to the inventionThe advantages are as follows:
(1) the doping gas of the N-type doped microcrystalline silicon film is carbon dioxide (CO) 2 ) To dinitrogen monoxide (N) 2 O), the crystallinity of the film is improved under the same power of 4000W, the refractive index can be easily matched to a better range, and lower resistivity and higher film crystallization rate can be maintained, so that the N-type doped microcrystalline silicon film with excellent performance is judged.
(2)N 2 O gas has oxidizing property and lower bonding energy, and can be dissociated at lower power output by CVD power supply than CO 2 The gas can use lower power to obtain the same oxygen content, so that the production cost is reduced and the energy is saved.
(3) When the N-type doped microcrystalline silicon film is doped with carbon dioxide, higher hydrogen is required to be diluted to obtain better crystallinity, and the doping is replaced by N 2 After O, because the influence of nitrogen elements on the crystallinity is not as large as that of carbon elements, the crystallinity of the N-type doped microcrystalline silicon film can be ensured by maintaining the matched hydrogen at low flow, so that the hydrogen consumption is reduced, the cost is reduced, and the energy is saved. For example, as shown in table 2, one row of the comparative examples in table 2 is a general process region when the N-type doped microcrystalline silicon thin film is doped with carbon dioxide gas, and when the carbon dioxide gas is replaced with nitrous oxide gas, the optimized parameters can be seen in one row of the examples in table 2, it can be seen that the amount of hydrogen used in the process and the power of the equipment are greatly reduced, the cost can be effectively saved, and the requirements of photovoltaic energy conservation and environmental protection are met.
TABLE 2 cost comparison of examples and comparative examples
Detailed description of the preferred embodiments SiH 4 (sccm) H 2 (sccm) N 2 O(sccm) SiH 4 /CO 2 Power(W) Refractive index n
Comparative example 50-300 10000-50000 10-600 0.1-2 3000-8000 2.7-3.3
Examples 50-300 3000-30000 10-150 0.1-0.5 1000-5000 2.4-3.0
In addition, in order to make the gas more dissociated, the microcrystalline dopant gas is separated from carbon dioxide (CO) 2 ) To dinitrogen monoxide (N) 2 O), the doping proportion of the nitrous oxide is reduced to about 20 percent. As can be seen from Table 1, when the doping ratio of dinitrogen monoxide is 10% to 30%, the refractive index of the film is greatly decreased, and it is confirmed that oxynitride in dinitrogen monoxide can be more efficiently incorporated into the film, and in this case, crystallinity is effectively satisfied, that is, 42% to 59% at a low refractive index (2.45 to 2.56)The temperature is increased to 55 to 72 percent.
For the test of the crystallinity, it should be emphasized that, in examples 1 to 8 and comparative examples 1 to 5, the cell was tested, and the raman test used a research and development machine, and the cell included the N-type monocrystalline silicon substrate 1, and the film thickness was relatively thick, so the raman crystallinity was relatively high. In order to compare the crystallinity of the N-type doped microcrystalline silicon oxide thin film 3, the invention also provides an example 9 and a comparative example 6, and the Raman spectra of the two embodiments are tested by using a mass production machine, so that the measurement mode is a practical mode of same mass production, specifically, 6nm of amorphous silicon is plated on a glass substrate, and then 20nm to 30nm of the N-type doped microcrystalline silicon oxide thin film 3 is plated on the 6nm of amorphous silicon, so that the measured crystallization rate is lower than that of the examples 1 to 8 and the comparative examples 1 to 5. The relevant parameters and the crystallization rates of the production processes of example 9 and comparative example 6 are shown in Table 1, the production methods are substantially the same as those of the foregoing comparative examples and examples, and it can be seen from Table 1 that the production method of the present invention is effective in increasing the crystallization rate of the N-type doped microcrystalline silicon oxide thin film 3.
Table 3 comparison of cell performance of examples and comparative examples
Type (B) Eff Voc lsc FF
Comparative example 100.00％ 100.00％ 100.00％ 100.00％
Examples 100.80％ 100.02％ 100.35％ 100.43％
In order to test the performance of the heterojunction solar cell of this embodiment, a series resistance test, a uniformity test, and a conversion efficiency, a voltage, a current, and a fill factor test were also performed on the cell, as shown in table 3. In the case of optimization of both comparative example 5 and example 5, dinitrogen monoxide (N) was used in the examples according to the invention 2 O) the conversion efficiency when doping gas can be increased by 0.8%, the current and the filling factor of the battery are greatly improved, and the performance of the battery is further improved.
For the series resistance, reference is made to fig. 2 and 8, which illustrate comparative example 6 and example 9, where each of the smallest squares represents a group of batteries formed in series, and the multiple squares represent different batteries on the production line. The battery packs at a plurality of specific positions are tested for series resistance and the variance is calculated, so that the uniformity of the series resistance Rs of the battery manufactured by the embodiment of the invention is better improved compared with the uniformity of the battery Rs of a comparative example, the uniformity value of the series resistance is reduced from 18% to 5%, and the highest value of the series resistance is also reduced, which is beneficial to the control of the electrical property of the battery on a production line.
Basically, the reduction and the improvement of uniformity of the resistance are also due to the improvement of the crystallinity of the N-type doped microcrystalline silicon thin film, the response of crystal lattices is measured by using Raman when the crystallinity of the microcrystalline is judged, and the crystallinity of the thin film can be judged by a response value at a certain wavelength. Thus, we use N 2 O instead of CO 2 The changes in crystallinity under the conditions of the two alternatives were compared.
With reference to FIGS. 3 to 7 and 9 to 13In contrast, FIGS. 3-7 illustrate the use of CO 2 The raman double peak fitting results of fig. 2 were tested at five positions with uniform sampling points, respectively, and it can be seen that the uniformity is poor. FIGS. 9 to 13 show the use of N 2 According to the Raman result of O, the crystallinity of the center point is improved from 32% to about 36%, and the crystallinity of the edge is greatly improved, which corresponds to the improvement of the conductivity; and the value of the uniformity of crystallization is reduced from 18.7% to 11.6%, i.e., the uniformity is improved, which corresponds to the uniformity of the resistance. From this, it can be judged that improvement of crystallinity is favorable for improvement of conductivity of the photovoltaic cell, and improvement of uniformity of crystallization is favorable for improvement of resistance uniformity or conductivity uniformity of the photovoltaic cell.
The invention has been described in detail hereinabove with reference to specific exemplary embodiments thereof. It will, however, be understood that various modifications and changes may be made without departing from the scope of the invention as defined in the appended claims. The detailed description and drawings are to be regarded as illustrative rather than restrictive, and any such modifications and variations are intended to be included within the scope of the present invention as described herein. Furthermore, the background is intended to be illustrative of the state of the art as developed and the meaning of the present technology and is not intended to limit the scope of the invention or the application and field of application of the invention.
More specifically, although exemplary embodiments of the invention have been described herein, the invention is not limited to these embodiments, but includes any and all embodiments modified, omitted, combined, e.g., between various embodiments, adapted and/or substituted, as would be recognized by those skilled in the art from the foregoing detailed description. The limitations in the claims are to be interpreted broadly based the language employed in the claims and not limited to examples described in the foregoing detailed description or during the prosecution of the application, which examples are to be construed as non-exclusive. Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims. The scope of the invention should, therefore, be determined only by the appended claims and their legal equivalents, rather than by the descriptions and examples given above.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. When flow, power, refractive index, time, or other value or parameter is expressed as a range, preferred range, or as a range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, a range of 1 to 50 should be understood to include any number, combination of numbers, or subrange selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, and all fractional values between the above integers, e.g., 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. With respect to sub-ranges, specifically consider "nested sub-ranges" that extend from any endpoint within the range. For example, nested sub-ranges of exemplary ranges 1-50 may include 1-10, 1-20, 1-30, and 1-40 in one direction, or 50-40, 50-30, 50-20, and 50-10 in another direction.

Claims (10)

1. A preparation method of N-type doped oxidation microcrystalline silicon is used for a solar cell and is characterized in that silane, hydrogen, N-type doping source gas and nitrous oxide are mixed for CVD reaction, and N-type doped oxidation microcrystalline silicon is obtained through deposition; the N-type doping source gas comprises Va group and/or VIA group elements.
2. The method for preparing N-type doped microcrystalline silicon oxide as claimed in claim 1, wherein the flow ratio of nitrous oxide and silane is 10% -60%.
3. The method for preparing N-type doped microcrystalline silicon oxide according to claim 1, comprising the following steps:
(1) putting the silicon substrate into a cavity of CVD equipment, and vacuumizing the CVD equipment;
(2) introducing silane, hydrogen, an N-type doping source gas and nitrous oxide into a vacuum cavity of the CVD equipment according to the preset reaction gas dosage;
(3) and (3) starting a power supply of the CVD equipment to dissociate the gas in the step (2) to form plasma type atoms, and depositing the plasma type atoms on the silicon substrate after the plasma type atoms are combined to obtain the N-type doped microcrystalline silicon oxide.
4. The method as claimed in claim 3, wherein in step (2), the silane is used in an amount of 50sccm to 300sccm, the hydrogen gas is used in an amount of 3000sccm to 30000sccm, the nitrous oxide is used in an amount of 10sccm to 150sccm, and the N-type doping source gas comprises phosphine in an amount of 250sccm to 1500 sccm.
5. The method according to claim 3, wherein in the step (3), the power output is not less than 1000W, and the deposition time is 1-5 min.
6. The method for preparing N-type doped microcrystalline silicon oxide as claimed in claim 2, wherein the flow ratio of nitrous oxide and silane is 10% -30%.
7. An N-type doped microcrystalline silicon oxide, which is prepared by the method for preparing an N-type doped microcrystalline silicon oxide according to any one of claims 1 to 6.
8. A heterojunction solar cell comprising a first silicon layer and a second silicon layer; the first silicon layer is an N-type doped microcrystalline silicon oxide as defined in claim 7, the second silicon layer comprises a crystalline silicon or an amorphous silicon layer or a microcrystalline silicon having a different doping amount or type from the first silicon layer, and the first silicon layer is disposed on the second silicon layer with a space charge region therebetween.
9. The heterojunction solar cell of claim 8, comprising a back electrode, a TCO thin film, a P-type doped microcrystalline silicon thin film, an intrinsic amorphous silicon thin film, an N-type monocrystalline silicon, an intrinsic amorphous silicon thin film, an N-type doped oxidized microcrystalline silicon, a TCO thin film and a front electrode connected in sequence along a thickness direction.
10. A method for manufacturing a heterojunction solar cell, wherein the heterojunction solar cell is the heterojunction solar cell according to claim 8 or 9, and the method comprises the following specific steps:
(1) depositing intrinsic amorphous silicon thin films on two sides of the N-type monocrystalline silicon by a PECVD method;
(2) depositing the N-type doped microcrystalline silicon oxide on the intrinsic amorphous silicon thin film on the front side of the N-type monocrystalline silicon by a PECVD method, and depositing a P-type doped microcrystalline silicon thin film on the intrinsic amorphous silicon thin film on the back side of the N-type monocrystalline silicon;
(3) depositing TCO thin films on two sides of the thin film obtained in the step (2) by a PVD method;
(4) and finally, printing silver electrodes on two sides of the thin film obtained in the step (3) by a screen printing method to obtain the heterojunction solar cell.
CN202210480356.4A 2022-05-05 2022-05-05 N-type doped oxide microcrystalline silicon, heterojunction solar cell and preparation methods of N-type doped oxide microcrystalline silicon and heterojunction solar cell Pending CN114843175A (en)

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