DE4408791B4 - Process for producing a silicon oxide semiconductor film - Google Patents
Process for producing a silicon oxide semiconductor film Download PDFInfo
- Publication number
- DE4408791B4 DE4408791B4 DE4408791A DE4408791A DE4408791B4 DE 4408791 B4 DE4408791 B4 DE 4408791B4 DE 4408791 A DE4408791 A DE 4408791A DE 4408791 A DE4408791 A DE 4408791A DE 4408791 B4 DE4408791 B4 DE 4408791B4
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- silicon oxide
- oxide semiconductor
- semiconductor film
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000004065 semiconductor Substances 0.000 title claims abstract description 10
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 14
- 229910021424 microcrystalline silicon Inorganic materials 0.000 claims abstract description 6
- 230000031700 light absorption Effects 0.000 claims description 13
- 230000003287 optical effect Effects 0.000 claims description 7
- 239000010408 film Substances 0.000 description 41
- 239000010410 layer Substances 0.000 description 22
- 239000007789 gas Substances 0.000 description 19
- 229910021417 amorphous silicon Inorganic materials 0.000 description 12
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 230000007423 decrease Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0376—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including amorphous semiconductors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/075—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PIN type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/548—Amorphous silicon PV cells
Abstract
Verfahren zur Herstellung eines Siliciumoxidhalbleiterfilms, der sich aus einem amorphen Siliciumoxid zusammensetzt, welcher eine mikrokristalline Siliciumphase enthält, dadurch gekennzeichnet, daß der Film durch Zersetzen eines Materialgases enthaltend wenigstens SiH4, CO2 und H2 mit einem CO2/(SiH4 + CO2)-Strömungsratenverhältnis von 0,6 oder weniger hergestellt wird.A process for producing a silicon oxide semiconductor film composed of an amorphous silica containing a microcrystalline silicon phase, characterized in that the film is formed by decomposing a material gas containing at least SiH 4 , CO 2 and H 2 with a CO 2 / (SiH 4 + CO 2 ) flow rate ratio of 0.6 or less.
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung eines Siliciumoxidhalbleiterfilms, der als Fensterschicht in einer fotovoltaischen Zelle aus amorphem Silicium (a-Si) geeignet ist.The The present invention relates to a process for producing a Silicon oxide semiconductor film serving as a window layer in a photovoltaic Cell of amorphous silicon (a-Si) is suitable.
Eine
fotovoltaische Zelle mit a-Si als Hauptmaterial, das durch Glimmentladungszersetzung
eines Materialgases oder einen Foto-CVD-ProzeB hergestellt wurde,
zeichnet sich durch einen Dünnfilmaufbau
sowie dadurch aus, daß leicht
eine große
Oberfläche
erzielbar ist und die Herstellungskosten gering sind. Bei fotovoltaischen
Zellen diese Art handelt es sich meistens um PIN-Zellen mit PIN-Übergängen.
Foto-Ladungsträger, die
hier zur Energieerzeugung beitragen, werden hauptsächlich in
der i-Schicht erzeugt, während
die p-Schicht und
die n-Schicht tote Schichten bleiben. Zur Erhöhung der Ausgangsleistung einer
fotovoltaischen Zelle, bei der das Licht über die p-Schicht
Aus einem kürzlichen Bericht ergibt sich, daß in einen amorphen Siliciumcarbidfilm (a-SiC), dem Kohlenstoffatome zugesetzt wurden, erfolgreich eine mikrokristalline Phase eingeschlossen wurde, und zwar durch Verwendung des in der JP 64-051618 A beschriebenen ECR-CVD-Verfahrens oder des Plasma-CVD-Verfahrens, das in „Characterization of High-Conductive p-Type a-SiC:H Produced by Highly Hydrogen Dilution" von Kenichi Hanaki et al. in der Druckschrift "Technical Digest of the International PVSEC-3 (1987), Seite 49 beschrieben ist. Ein solcher Film hat infolge seiner a-SiC-Phase, die die mikrokristalline Si-Phase enthält, eine höhere Lichtleitfähigkeit und bessere elektrische Eigenschaften.Out a recent one Report shows that in an amorphous silicon carbide film (a-SiC), the carbon atoms were added, successfully including a microcrystalline phase was described by using the in JP 64-051618 A. ECR-CVD method or the plasma CVD method described in "Characterization of High-Conductive p-Type a-SiC: H Produced by Highly Hydrogen Dilution "by Kenichi Hanaki et al. in the publication "Technical Digest of the International PVSEC-3 (1987), page 49 is. Such a film has due to its a-SiC phase, the microcrystalline Si phase contains a higher one photoconductivity and better electrical properties.
Dadurch, daß man den a-Si-Film so ausbildet, daß er die mikrokristalline Si Phase enthält, wie oben beschrieben, wird die Lichtleitfähigkeit erhöht, die abzunehmen neigt, wenn Atome von Elementen anderer Art zur Erweiterung der optischen Lücke zugesetzt werden. Dies ist also ein vielversprechendes Verfahren zur Verbesserung der Eigenschaften der Fensterschicht der fotovoltaischen Zelle. Das bekannte Verfahren zur Mikrokristallisierung des a-SiC-Films ist jedoch schwierig industriell umzusetzen, da es die Filmherstellungsbedingungen für die Mikrokristallisation auf einen engen Bereich begrenzt und es darüberhinaus schwierig macht, die Abscheidungsrate zu erhöhen.Thereby, that he the a-Si film is formed so that he containing the microcrystalline Si phase as described above the light conductivity elevated, which tends to decrease when atoms of elements of other kind expand the optical gap be added. So this is a promising process to improve the properties of the window layer of the photovoltaic Cell. The known method for microcrystallization of the a-SiC film However, it is difficult to implement industrially because of the film manufacturing conditions for the Microcrystallization limited to a narrow range and beyond difficult to increase the deposition rate.
Aufgabe der vorliegenden Erfindung ist es, ein Verfahren zur Herstellung eines Films zu schaffen, mit dem industriell ein Siliciumoxid-(SiO)-Halbleiterfilm mit einem niedrigen Lichtabsorptionskoeffizienten und hoher Lichtleitfähigkeit geschaffen werden kann, der in auf a-Si-basierenden Filmen einen amorphen mikrokristallisierten Siliciumoxidfilm (a-SiO) aufweist, der ein Oxid enthält.task The present invention is a process for the preparation of a film industrially using a silica (SiO) semiconductor film with a low light absorption coefficient and high light conductivity which can be created in a-Si based films having amorphous microcrystallized silicon oxide film (a-SiO), which contains an oxide.
Diese Aufgabe wird erfindungsgemäß durch ein Verfahren gemäß Patentanspruch 1 gelöst.These Task is achieved by a method according to claim 1 solved.
Dabei wird in dem Materialgas eine Glimmentladung erzeugt, um die Gasmischung bei einer hochfrequenten Leistungsdichte von 40 mW/cm2 oder mehr zu zersetzen. Der Lichtabsorptionskoeffizient für Licht einer Wellenlänge von 340 nm oder mehr in dem erhaltenen SiO Halbleiterfilm beträgt 106 cm–1 oder weniger, und die Lichtleitfähigkeit liegt bei 10–6 S/cm oder mehr. Darüberhinaus ist es wirksam, als eine Fensterschicht in der fotovoltaischen Zelle einen p-leitenden oder einen n-leitenden Film zu benutzen, der durch Mischen des Materialgases mit einem Dotierungsgas erhalten wird.In this case, a glow discharge is generated in the material gas in order to decompose the gas mixture at a high-frequency power density of 40 mW / cm 2 or more. The light absorption coefficient for light of a wavelength of 340 nm or more in the obtained SiO 2 semiconductor film is 10 6 cm -1 or less, and the optical conductivity is 10 -6 S / cm or more. Moreover, it is effective to use as a window layer in the photovoltaic cell a p-type or n-type film obtained by mixing the material gas with a doping gas.
Das Herstellen einer Fensterschicht für eine fotovoltaische Zelle unter Verwendung eines SiH4, Co2 und H2 enthaltenden Materialgases ist in der zuvor genannten JP 61-242085 A beschrieben, wobei der Wert des Gasströmungsratenverhältnisses von Co2 zu (SiH4 + Co2) 0,83 beträgt, und der erhaltene a-Si-Film Sauerstoffatome und Kohlenstoffatome enthält. Wenn dagegen das genannte Verhältnis 0,6 oder weniger beträgt, liegt der Kohlenstoffanteil unterhalb der Meßgrenze, insbesondere bei einem Film, der durch eine Glimmentladung bei einer hochfrequenten Leistungsdichte von 40 mW/cm2 oder mehr erhalten wurde, und der Film wird zu einer SiO-Phase, die eine mikrokristallisierte Si Phase und eine a-SiO-Phase enthält und einen hohen Lichtabsorptionskoeffizienten bei einer Lichtleitfähigkeit von mehr als 10–6 S/cm aufweist.Producing a window layer for a photovoltaic cell using a SiH 4 , Co 2 and H 2 -containing material gas is described in the aforementioned JP 61-242085 A, wherein the value of the gas flow rate ratio of Co 2 to (SiH 4 + Co 2 ) is 0.83, and the obtained a-Si film contains oxygen atoms and carbon atoms , On the other hand, when said ratio is 0.6 or less, the carbon content is below the measurement limit, particularly, a film obtained by a glow discharge at a high-frequency power density of 40 mW / cm 2 or more, and the film becomes SiO Phase containing a microcrystallized Si phase and an α-SiO phase and having a high light absorption coefficient at a photoconductivity of more than 10 -6 S / cm.
Ausführungsbeispiele der Erfindung werden nachfolgend anhand der Zeichnungen näher erläutert. Es zeigen:embodiments The invention will be explained in more detail with reference to the drawings. Show it:
Unter
den folgenden Bedingungen wurden p-leitende und n-leitenden SiO-Filme
hergestellt: Mischen von SiH4, CO2 und H2, Zusetzen
von B2H6 oder PH3 als Dotierungsgas zu dem Materialgas und
Variieren des Strömungsratenverhältnisses
für die
einzelnen Gase:
Messungen der Raman-Streuung an dem auf diese Weise erhaltenen SiO-Film ergaben, daß eine Spitze bei etwa 530 cm–1 vorhanden ist, was die Existenz von Si-Kristallen in den Raman-Spektren und die Koexistenz der mikrokristallinen Si-Phase und der a-SiO-Phase. Es bestätigte sich, daß die Stärke der Spitze bei etwa 530 cm–1 mit zunehmendem CO2/(SiH4 + CO2) Strömungsratenverhältnis abnimmt.Raman scattering measurements on the SiO 2 film obtained in this way revealed that a peak is present at about 530 cm -1 , indicating the existence of Si crystals in the Raman spectra and the coexistence of the microcrystalline Si phase and the Si a-SiO phase. It was confirmed that the thickness of the tip at about 530 cm -1 decreases with increasing CO 2 / (SiH 4 + CO 2 ) flow rate ratio.
Filme, die unter Verwendung von C2H2 anstelle von CO2 unter denselben Bedingungen, mit Ausnahme des Materialgases, wie in der oben beschriebenen Ausführungsform hergestellt worden, zeigten keine Raman-Spektren mit einer Spitze bei etwa 530 cm–1 (die die Existenz einer Si-Kristallphase anzeigen würde) und waren nicht mikrokristallisiert, obwohl der Kohlenstoffanteil in den erhaltenen Filmen nur 20 % bezogen auf das Atomgewicht betrug. Diese Tatsache deutet an, daß die Kohlenstoffatome die Mikrokristallisation des Siliciums wirksamer verhindern als die Sauerstoffatome, und es hat sich gezeigt, daß die so hergestellten Filme nicht als Material für die Fensterschicht in der fotovoltaischen Zelle geeignet sind, und zwar wegen der Abnahme der Lichtleitfähigkeit, selbst wenn der Lichtabsorptionskoeffizient durch Verwendung größerer Lücken verringert wäre.Films prepared using C 2 H 2 instead of CO 2 under the same conditions, except for the material gas, as in the embodiment described above, did not show Raman spectra with a peak at about 530 cm -1 (indicating existence Si crystal phase) and were not microcrystallized although the carbon content in the obtained films was only 20% by atomic weight. This fact indicates that the carbon atoms prevent the microcrystallization of the silicon more effectively than the oxygen atoms, and it has been found that the films thus prepared are not suitable as a material for the window layer in the photovoltaic cell because of the decrease of the photoconductivity. even if the light absorption coefficient were reduced by using larger gaps.
Durch die vorliegende Erfindung ist es möglich geworden, einen SiO-Film mit einer a-SiO-Phase zu schaffen, der eine Si mikrokristalline Phase aber keinen Kohlenstoff enthält. Für den a-SiO-Film verwendet CO2 mit einem niedrigen Mischungsverhältnis als Sauerstoffquelle und eine Gasmischung aus SiH4 und H2 zur Erzeugung einer mikrokristallisierten Si-Phase verwendet. Als Folge kann ein auf a-Si basierender Film erzeugt werden, der einen geringen Lichtabsorptionskoeffizienten aufweist, und zwar als Folge der Verwendung breiterer optischer Lücken durch Sauerstoffatome, sowie eine hohe Lichtleitfähigkeit als Folge der Existenz der mikrokristallisierten Phase. Daher kann der Film sehr wirksam für die p-leitende oder n-leitende Fensterschicht in einer auf a-Si basierenden fotovoltaischen Zelle eingesetzt werden.By the present invention, it has become possible to provide a SiO film having an a-SiO phase containing a microcrystalline Si phase but no carbon. For the a-SiO 2 film, CO 2 having a low mixing ratio uses as an oxygen source and a gas mixture of SiH 4 and H 2 is used for producing a microcrystallized Si phase. As a result, an a-Si based film having a low light absorption coefficient can be produced as a result of using wider optical gaps by oxygen atoms, as well as a high light conductivity due to the existence of the microcrystallized phase. Therefore, the film can be used very effectively for the p-type or n-type window layer in an a-Si based photovoltaic cell.
Claims (7)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP54433/93 | 1993-03-16 | ||
JP5054433A JP3047666B2 (en) | 1993-03-16 | 1993-03-16 | Method for forming silicon oxide semiconductor film |
Publications (2)
Publication Number | Publication Date |
---|---|
DE4408791A1 DE4408791A1 (en) | 1994-09-22 |
DE4408791B4 true DE4408791B4 (en) | 2006-10-19 |
Family
ID=12970584
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE4408791A Expired - Fee Related DE4408791B4 (en) | 1993-03-16 | 1994-03-15 | Process for producing a silicon oxide semiconductor film |
Country Status (2)
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JP (1) | JP3047666B2 (en) |
DE (1) | DE4408791B4 (en) |
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-
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Also Published As
Publication number | Publication date |
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DE4408791A1 (en) | 1994-09-22 |
JPH06267868A (en) | 1994-09-22 |
JP3047666B2 (en) | 2000-05-29 |
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