CN102021538A - Film deposition method - Google Patents
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- CN102021538A CN102021538A CN 201010181234 CN201010181234A CN102021538A CN 102021538 A CN102021538 A CN 102021538A CN 201010181234 CN201010181234 CN 201010181234 CN 201010181234 A CN201010181234 A CN 201010181234A CN 102021538 A CN102021538 A CN 102021538A
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Abstract
The invention discloses a film deposition method, which comprises the following steps of: oppositely placing an anode plate and a cathode plate in parallel in a reaction chamber, wherein the surface of the cathode plate, which faces to the anode plate, is provided with a sacrifice layer; placing a conducted base plate or a base plate with a conduction layer on which the conduction layer contacts the surface of the anode plate on the surface of the anode plate, which faces to the sacrifice layer; introducing hydrogen; and building a direct-current electric field between the anode plate and the cathode plate, exciting the hydrogen into a plasma and etching the sacrifice layer, and depositing a film which is based mainly on sacrifice layer substances on the surface of the base plate. By using the method, raw material gas including film substances does not need providing from outside, and the direct-current electric field is used for excitation, which greatly simplifies equipment and process for manufacturing large-area microcrystalline silicon photoelectric devices.
Description
Technical field
The present invention relates to the photovoltaic solar cell technical field, particularly a kind of membrane deposition method.
Background technology
Along with the worsening shortages of the energy, the development and use of renewable green energy resource more and more are subjected to people's attention, are subjected to common people's attention especially especially with the utilization of sun power.As the solar cell of solar energy converting media, the silicon-based film solar cells that occurs in recent years particularly is with its big area, low cost, can deposit and be easy to lay the development trend that advantage such as installation is being represented photovoltaic technology on frivolous substrate.
The transform light energy that thin-film solar cells is used for light sources such as sunlight, light or fluorescence are sent is an electric energy, this conversion is that photovoltaic (photoelectricity) effect by semiconductor material produces, when irradiate light when the thin-film solar cells, absorbed by the semiconductor active layer and produce photic current carrier.In order to collect photic current carrier effectively, silicon-based film solar cells is configured to p-i-n type structure usually, and wherein the p layer is a light incident layer, the i layer be the intrinsic absorption layer and be in the p layer and built in field that the n layer is set up in.Incident light enters the i layer by p layer or n layer, produces electron-hole pair in the i layer, and photic current carrier is in case just separated by built in field after producing, hole drift is to p layer side, electronic drift forms photogenerated current and photovoltage to n layer side, is drawn by preceding electrode and back electrode.
The thin-film solar cells of above-mentioned silica-base material can absorb the radiation in most of spectral range.But along with the growth of light application time, silica-base material is an example with the amorphous silicon material, and its photoelectricity conversion capability can fail gradually, promptly produces photic attenuating effect.Compare with non-crystalline silicon, the nanocrystal silicon (traditionally be commonly called microcrystal silicon) of band gap between 1.1-1.2eV also is a kind of ideal material of light absorbing zone, and nanocrystal silicon for a long time can keep satisfactory stability under the strong illumination, so nanocrystal silicon has become the general purpose material based on the film multijunction solar cell bear building-up photoelectric conversion unit light absorbing zone of silicon.Except that absorption layer, the tunnel recombination layer (tunnel junction) between multijunction solar cell knot and the knot also often adopts the nanocrystal silicon material.
The sedimentary traditional method of Nano silicon-crystal thin film is that using plasma strengthens chemical Vapor deposition process (PECVD) technology, Fig. 1 is the synoptic diagram of explanation plasma enhanced chemical vapor deposition process deposits film mode, as shown in Figure 1, be equipped with two opposite polarity parallel plate electrodes in the vacuum chamber 10, be respectively exciting electrode (negative electrode) 11 and ground-electrode (anode) 12, the zone 17 between them is that the excitation of plasma body forms the zone.Exciting electrode 11 places box cover 16, has inlet mouth 19 on box cover 16, and reactant gases enters vacuum chamber 10 by inlet mouth 19, and reacted residual gas is 18 discharges from the air outlet.Exciting electrode 11 has the through hole of suitable density, it places a shower plate 13 that links to each other with box cover 16 behind, be used for the distribution of plasma confinement precursor reactant gas and the flow direction of reactant gases (raw-gas mixture), can make reactant gases be delivered into whole plasma body zone 17 equably.Therefore substrate can not be placed in exciting electrode 11 surfaces, and substrate 15 is placed on ground-electrode 12 surfaces usually.Ground-electrode 12 back sides that are loaded with substrate 15 are equipped with a well heater 14, substrate 15 is reached and maintain in the range of set temperature.High frequency (comprising RF, VHF, UHF) power source provides energy for exciting electrode 11, is plasma body by glow discharge with reactant gases ionization, at substrate 15 surface deposition films.
Though pecvd process has the advantages that technology is simple, sedimentation effect is high, (for example area is greater than 0.7m at large-area substrates
2) during the large-area Nano silicon-crystal thin film of surface deposition, the consistence of rete and thickness evenness can significantly descend.Traditional in addition pecvd process is that reactant gases (the normally source gaseous mixture of silane and hydrogen) is provided to reaction chamber from the outside, reactant gases is difficult to guarantee at reaction chamber, distributing homogeneity especially for large-area substrates in the sedimentary large-scale reaction chamber (for example the patent No. is the large-scale PECVD depositing device described in 200820008274.5 the Chinese patent), and cause contaminating impurity easily, influence the homogeneity and the consistence of Nano silicon-crystal thin film.In addition, the electrode structure complexity of traditional PECVD equipment, and, need very big gas flow in order to obtain higher sedimentation rate and suitable degree of crystallization, gas consumption is very big.The complicacy of equipment and raw-material high flow rate improve production cost, and product competition obviously descends.
Summary of the invention
The object of the present invention is to provide a kind of membrane deposition method, be specially adapted to the deposition of Nano silicon-crystal thin film, can use simple PECVD depositing device to improve the homogeneity and the stability of big area depositing nano polycrystal silicon film.Method of the present invention is applicable to the deposition of all silica-base films, comprises silicon-germanium alloy film.
For achieving the above object, a kind of membrane deposition method provided by the invention comprises:
Parallel positive plate staggered relatively and negative plate in reaction chamber, described negative plate has sacrifice layer towards the surface of described positive plate;
Place conduction towards the surface of described sacrifice layer or have conductive layer and described conductive layer and the surperficial substrate that contacts of described positive plate at described positive plate;
Feed hydrogen;
Between described positive plate and negative plate, set up DC electric field, described hydrogen is excited be the described sacrifice layer of plasma etching, at the film of described substrate surface deposition based on the sacrifice layer material.
Optionally, add a small amount of other in the described hydrogen and contain the gas of etching composition.
Optionally, the material of described sacrifice layer comprises silica-base material.
Optionally, the step of setting up DC electric field comprises:
With described positive plate and substrate ground connection;
Negative plate connects negative DC voltage.
Optionally, the described gas that contains the etching composition comprises HF, SiFH
3, SiH
2Cl
2, F
2, Cl
2, HCl, NF
3In a kind of or the combination.
Optionally, described negative DC voltage value is-100 volts～-1500 volts.
Optionally, the described negative DC voltage galvanic current density that offers described negative plate is 0.1～3mA/cm
2
Optionally, the distance between described positive plate and the described negative plate comprises 1 centimetre～5 centimetres scope.
Optionally, the interior gaseous tension of described reaction chamber comprises the scope of 0.5～5Torr.
Optionally, also comprise rare gas element in the gaseous mixture.
Optionally, the concentration of the described gas that contains the etching composition is less than 5%.
Optionally, the gas that also comprises phosphorous or boracic in described hydrogen or the gaseous mixture.
Optionally, described positive plate and negative plate apply one or more alternating electric fields respectively or simultaneously.
Optionally, between described positive plate and negative plate, place a mesh electrode plate.
Optionally, described positive plate, negative plate and described mesh electrode plate apply one or more alternating electric fields respectively or simultaneously.
Optionally, described alternating electric field is provided by the power supply that comprises low frequency, radio frequency (RF), extremely-high frequency (VHF).
Compared with prior art, the present invention has the following advantages:
Membrane deposition method of the present invention utilizes the asymmetry of hydrogen gas plasma anticathode and anode surface corrasion in the DC electric field, when producing hydrogen direct current glow discharge, suitable air pressure, power density and negative electrode to substrate surface apart under the situation, sacrifice layer on the negative plate is by the high speed etching, produce the predecessor (precursors) of sacrifice layer material by the etching of anticathode surface sacrifice layer, be diffused on the substrate of anode surface the formation of deposits film.This shows, the deposition predecessor of membrane deposition method of the present invention is not to obtain by the raw gas that ionization provides in reaction chamber from the outside, but obtain by the sedimentary in advance sacrifice layer of etching cathode surface, therefore reduced the pollution probability of foreign matter to a great extent to film.Saved a large amount of reactant gasess simultaneously, for example silane (when the depositing silicon base film) greatly reduces manufacturing cost.
Since adopt DC electric field to carry out plasma exciatiaon, more simple and reliable more than normally used high frequency plasma excitation process, have very high repeatability.And ununiformity and great energy waste from having avoided the high frequency excitation electric field in essence.
In addition, because the predecessor of deposit film results from the etching of anticathode surface sacrifice layer, as long as satisfy the parallelism requirement between substrate and the negative plate, the present invention just can fundamentally solve the particularly sedimentary homogeneity question of bulk silicon base film of large area film, is very beneficial for implementing in large vacuum coating equipment in mode cheaply the uniform deposition of bulk silicon base film (particularly Nano silicon-crystal thin film).
Description of drawings
By the more specifically explanation of the preferred embodiments of the present invention shown in the accompanying drawing, above-mentioned and other purpose, feature and advantage of the present invention will be more clear.Reference numeral identical in whole accompanying drawings is indicated identical part.Painstakingly do not draw accompanying drawing in proportion, focus on illustrating purport of the present invention.In the accompanying drawings, for cheer and bright, amplified the thickness of layer.
Fig. 1 strengthens the synoptic diagram of chemical vapor deposition method deposit film mode for traditional plasma;
Fig. 2 to Fig. 6 is the reaction chamber structure synoptic diagram of explanation membrane deposition method of the present invention.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, the specific embodiment of the present invention is described in detail below in conjunction with accompanying drawing.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement much to be different from alternate manner described here, and those skilled in the art can do similar popularization under the situation of intension of the present invention.Therefore the present invention is not subjected to the restriction of following public concrete enforcement.
Be example with the depositing silicon base film below, membrane deposition method of the present invention be described in detail in conjunction with Fig. 2 to Fig. 6.According to embodiments of the invention, utilize the asymmetry of hydrogen gas plasma anticathode and anode surface corrasion under the direct current glow discharge environment, by the silicon materials of hydrogen gas plasma etching cathode surface at anode surface depositing silicon film.Specifically, at parallel negative electrode (cathode staggered relatively, usually connect the output terminal of direct supply) and anode (anode, be generally ground-electrode) between apply sufficiently high volts DS (electric field), (direct-current plasma excites to utilize direct current glow discharge, dc glow-discharge) hydrogen is excited be plasma body, the silica-base material sacrifice layer of etching cathode surface also can be with the full wafer silicon chip as sacrifice layer.In the DC electric field, near the negative electrode hydrogen atom density will be higher than near the hydrogen atom density the anode, therefore cathode surface to bear than anode surface strong the etching of Duoing, the gas phase predecessor (precursors) of the sacrificial layer material peeled off of being etched is diffused into formation of deposits film on the substrate of anode surface.In fact, in negative electrode and anode surface etching and sedimentation is simultaneous, in other words, under the direct current glow discharge condition, exist sacrificial layer material to be etched to form the gentle phase predecessor of process of gas phase predecessor to deposit to process on the sacrifice layer again at cathode surface; The process that exists the gentle phase predecessor of gas phase predecessor formation of deposits film from film, to be etched away again at anode surface.That is to say, have etching simultaneously and deposit two processes again at negative electrode and anode surface, and etching and to deposit these two processes again are two processes of vying each other.Under proper condition, for example sufficiently high discharge power, gaseous tension and suitable negative electrode and the spacing between the anode, in the gas that feeds under the sufficiently high situation of concentration of hydrogen, at cathode surface, etch rate is higher than sedimentary speed far away again, therefore the predecessor moment that deposits back sacrifice layer is etched away again, then is that sedimentary speed can be higher than etch rate far away at anode surface, and the predecessor moment that is etched away from film surface deposits back film again.Negative electrode and anode surface are for the asymmetry of hydrogen gas plasma etching in this DC electric field, make that in cathode surface etching and sedimentary cleaner effect be etching, in anode surface etching and sedimentary cleaner effect is deposition, has therefore just produced the thin film deposition on the anode surface substrate that is caused by etching cathode surface sacrifice layer.
At first as shown in Figure 2, method of the present invention is parallel positive plate 102 staggered relatively and negative plate 104 in reaction chamber 100 at first, distance between the two is 1～5 centimetre, the sacrifice layer 106 that has silicon materials at negative plate 104 towards the surface of positive plate 102, sacrifice layer 106 can adopt any deposition, for example utilize the mixed gas of silane and hydrogen, under selected arbitrarily air pressure, and under temperature arbitrarily, use plasma exciatiaon mode arbitrarily, comprise direct current, radio frequency (RF), extremely-high frequency (VHF) and very high frequency(VHF) (UHF) etc.Sacrifice layer 106 also is attached at the silicon thin plate material on negative plate 104 surfaces, such as silicon wafer (crystalline siliconwafer).
Then as shown in Figure 3, place substrate 108 at described positive plate 102 towards the surface of sacrifice layer 106, substrate 108 must be an electro-conductive material, or the surface is coated with the material of conductive film, conductive film contacts with positive plate 102, so that substrate 108 keeps identical current potential with positive plate 102.Subsequently, feed hydrogen, in other embodiments, except that hydrogen, can also add argon gas rare gas elementes such as (Ar).Before feeding hydrogen, utilize the conventional means that vacuumize that the air in the reaction chamber is discharged.In other embodiments, can also add a spot of gas that contains the etching composition in the hydrogen, for example HF, SiFH
3, SiH
2Cl
2, F
2, Cl
2, HCl, NF
3In a kind of or the combination, the described concentration that these contain etching composition gas is less than 5%.
With positive plate 102 ground connection, apply negative DC voltage to negative plate 104, the negative DC voltage value is-100～-1500 volts, galvanic current density (dc current density) is 0.1～3mA/cm
2Between positive plate 102 and negative plate 104, set up DC electric field.Hydrogen is ionized to plasma body carries out etching to described sacrifice layer 106, and the silicon matter that etching is peeled off diffuses to substrate 108 surfaces, at substrate 108 surface deposition films.Reaction chamber 100 gas inside pressure remain on 0.5～5torr in the deposition process, 0.6～2.0torr for example, and the temperature maintenance of substrate 108 is at 100～300 ℃.
Under the effect of DC electric field, the zone between positive plate 102 and the negative plate 104 produces direct current glow discharge, and hydrogen or hydrogenous mixed gas are ionized and are plasma body, form hydrogeneous plasma cloud 110, as shown in Figure 4.The hydrogen gas plasma density that will be higher than positive plate 102 near surfaces in the hydrogen gas plasma density of negative plate 104 near surfaces, the atomic hydrogen density on negative plate 104 surfaces is higher than positive plate 102 surfaces far away, so when hydrogen was excited to plasma body formation plasma cloud 110 by DC electric field, the corrasion that the sacrifice layer 106 on negative plate 104 surfaces will bear was much stronger than the substrate 108 on positive plate 102 surfaces.The Siliciumatom particle that breaks away from the Siliciumatom particle of sacrifice layer 106 and disengaging substrate 108 surfaces that are etched though be etched all can deposit respectively once more with higher probability and speed gets back to sacrifice layer 106 and substrate 108 surfaces, but because the asymmetry of corrasion, the Siliciumatom that deposits back sacrifice layer 106 once more is etched away rapidly again.Therefore, the asymmetry of corrasion, sacrifice layer 106 continuous attenuates, the clean effect that is produced is at the continuous formation of deposits silica-base film 112 of substrate 108 surface silicon atoms particles, as shown in Figure 5.
Along with the continuation of etching, by the asymmetry of this direct current glow discharge institute inherent plasma etching, sacrifice layer 106 is etched away, and forms silica-base film 112 at substrate 108 surface depositions, as shown in Figure 6.
In other embodiments of the invention, also add the gas of phosphorous or boracic in hydrogen or the hydrogen-containing gas mixture, thereby at substrate 108 surface deposition n types or p type silica-base film.
In other embodiments of the invention, when applying DC electric field, positive plate 102 and negative plate 104 also can apply one or more alternating electric fields respectively, and perhaps positive plate 102 and negative plate 104 apply one or more alternating electric fields simultaneously.
In other embodiments of the invention, between positive plate 102 and negative plate 104, also place a mesh electrode plate (not shown), in the case, positive plate 102, negative plate 103 and this mesh electrode plate can be respectively or are applied one or more alternating electric fields simultaneously.
Described alternating electric field is provided by the power supply that comprises low frequency, radio frequency (RF), extremely-high frequency (VHF).
Membrane deposition method of the present invention is different from traditional pecvd process, also is different to comprise sputter coating method (sputtering) and evaporation coating method physical vapor deposition (Physical Vapor Deposition, PVD) methods such as (Evaporation).Traditional pecvd process be from the outside with the mixed reactant gases input reaction chamber of raw gas (for example silane) and hydrogen, utilize radio frequency glow discharge with reactant gases ionization for plasma body at the substrate surface deposit film.The sputter coating method is to utilize direct current or high-frequency electric field to make rare gas element (being generally argon) that ionization take place, and the high-energy positive ion that ionization produces bombards target at a high speed, and atom or molecule on the target are sputtered out, and deposits to then and forms film on the substrate.Thermal evaporation or electron beam evaporation rely on high temperature deposited material are activated the disengaging evaporation source, then are deposited on the cryogenic relatively substrate.The activation process of the starting material (' target ' or ' evaporation source ') of PVD physical coating methods such as sputter, thermal evaporation or electron beam steaming does not rely on chemical reaction.
Membrane deposition method of the present invention is a kind of material transfer method that relies on plasma chemical reaction in essence, utilize the asymmetry of hydrogen gas plasma anticathode and anode surface corrasion in the DC electric field, by the sacrificial layer material of etching cathode surface on the substrate of anode surface deposit film.Method of the present invention does not need to provide raw gas from the outside in reaction chamber, has reduced the chance of contaminating impurity, has saved a large amount of reactant gasess simultaneously.Membrane deposition method of the present invention adopts DC electric field to carry out plasma exciatiaon, simple and reliable more than normally used radio frequency (RF) or extremely-high frequency (VHF) plasma exciatiaon process, has very high repeatability, from the ununiformity of having avoided high-frequency electric field to excite in essence.Because the predecessor of deposit film results from the etching of anticathode surface sacrifice layer, the size of substrate can be very big (substrate can be infinitely great in theory), as long as guarantee the parallelism between substrate and the negative plate, just can fundamentally improve in the deposition over large area substrates large area film homogeneity of Nano silicon-crystal thin film particularly.
The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction.Any those of ordinary skill in the art are not breaking away under the technical solution of the present invention scope situation, all can utilize the method and the technology contents of above-mentioned announcement that technical solution of the present invention is made many possible changes and modification, or be revised as the equivalent embodiment of equivalent variations.Therefore, every content that does not break away from technical solution of the present invention, all belongs in the protection domain of technical solution of the present invention any simple modification, equivalent variations and modification that above embodiment did according to technical spirit of the present invention.
Claims (16)
1. membrane deposition method comprises:
Parallel positive plate staggered relatively and negative plate in reaction chamber, described negative plate has sacrifice layer towards the surface of described positive plate;
Place conduction towards the surface of described sacrifice layer or have conductive layer and described conductive layer and the surperficial substrate that contacts of described positive plate at described positive plate;
Feed hydrogen;
Between described positive plate and negative plate, set up DC electric field, described hydrogen is excited be the described sacrifice layer of plasma etching, at the film of described substrate surface deposition based on the sacrifice layer material.
2. method according to claim 1 is characterized in that: add a small amount of other in the described hydrogen and contain the gas of etching composition.
3. method according to claim 1 is characterized in that: the material of described sacrifice layer comprises silica-base material.
4. method according to claim 1 is characterized in that: the step of setting up DC electric field comprises:
With described positive plate and substrate ground connection;
Negative plate connects negative DC voltage.
5. method according to claim 2 is characterized in that: the described gas that contains the etching composition comprises HF, SiFH
3, SiH
2Cl
2, F
2, Cl
2, HCl, NF
3In a kind of or the combination.
6. method according to claim 4 is characterized in that: described negative DC voltage value is-100 volts～-1500 volts.
7. method according to claim 4 is characterized in that: the galvanic current density that described negative DC voltage offers described negative plate is 0.1～3mA/cm
2
8. method according to claim 1 is characterized in that: the distance between described positive plate and the described negative plate comprises 1 centimetre～5 centimetres scope.
9. method according to claim 1 is characterized in that: the gaseous tension in the described reaction chamber comprises the scope of 0.5～5Torr.
10. method according to claim 2 is characterized in that: also comprise rare gas element in the gaseous mixture.
11. according to claim 2 or 5 described methods, it is characterized in that: the concentration of the described gas that contains the etching composition is less than 5%.
12. method according to claim 1 and 2 is characterized in that: the gas that also adds phosphorous or boracic in described hydrogen or the gaseous mixture.
13. method according to claim 1 is characterized in that: described positive plate and negative plate apply one or more alternating electric fields respectively or simultaneously.
14. method according to claim 1 is characterized in that: between described positive plate and negative plate, place a mesh electrode plate.
15. method according to claim 14 is characterized in that: described positive plate, negative plate and described mesh electrode plate apply one or more alternating electric fields respectively or simultaneously.
16. according to claim 13 or 15 described methods, it is characterized in that: described alternating electric field is provided by the power supply that comprises low frequency, radio frequency (RF), extremely-high frequency (VHF).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014663A (en) * | 2011-09-22 | 2013-04-03 | 吉富新能源科技(上海)有限公司 | Method for adjusting PECVD airflow outlet position for improving film uniformity under large area |
| CN110676353A (en) * | 2019-10-28 | 2020-01-10 | 成都晔凡科技有限公司 | Film coating device and method for manufacturing heterojunction solar cell and laminated assembly |
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| CN101245446A (en) * | 2007-02-14 | 2008-08-20 | 北京行者多媒体科技有限公司 | Method for improving homogeneity of large area film coating |
| CN101609858A (en) * | 2008-06-20 | 2009-12-23 | 福建钧石能源有限公司 | Membrane deposition method |
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| CN101245446A (en) * | 2007-02-14 | 2008-08-20 | 北京行者多媒体科技有限公司 | Method for improving homogeneity of large area film coating |
| CN101609858A (en) * | 2008-06-20 | 2009-12-23 | 福建钧石能源有限公司 | Membrane deposition method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103014663A (en) * | 2011-09-22 | 2013-04-03 | 吉富新能源科技(上海)有限公司 | Method for adjusting PECVD airflow outlet position for improving film uniformity under large area |
| CN110676353A (en) * | 2019-10-28 | 2020-01-10 | 成都晔凡科技有限公司 | Film coating device and method for manufacturing heterojunction solar cell and laminated assembly |
| CN110676353B (en) * | 2019-10-28 | 2024-04-26 | 通威太阳能(金堂)有限公司 | Coating device and method for manufacturing heterojunction solar cell and laminated tile assembly |
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Application publication date: 20110420 |