Method of manufacturing photoelectric conversion device

• US 8,207,011 B2
• Filed: 08/20/2010
• Issued: 06/26/2012
• Est. Priority Date: 08/25/2009
• Status: Expired due to Fees

• Current Assignee: Semiconductor Energy Laboratory Co., Ltd.
• Original Assignee: Semiconductor Energy Laboratory Co., Ltd.
• Inventors: Hiura, Yoshikazu, Yamazaki, Shunpei, Kataishi, Riho
• Primary Examiner(s): Dang, Phuc
• Application Number:
  US12/860,283
• Publication Number:
  US 20110053311A1
• Time in Patent Office: 676 Days
• Field of Search: 438/96, 438/97, 438/488, 257/E31.043, 136/255, 136/258
• US Class Current: 438/97
• CPC Class Codes: C23C 16/45557 Pulsed pressure or control pressure
• CPC Class Codes: C23C 16/45565 Shower nozzles
• CPC Class Codes: C23C 16/5096 Flat-bed apparatus
• CPC Class Codes: H01L 21/02532 Silicon, silicon germanium, germanium
• CPC Class Codes: H01L 21/0262 Reduction or decomposition of gaseous compounds, e.g. CVD
• CPC Class Codes: H01L 31/03921 including only elements of Group IV of the Periodic Table
• CPC Class Codes: H01L 31/046 PV modules composed of a plurality of thin film solar cells deposited on the same substrate
• CPC Class Codes: H01L 31/0463 characterised by special patterning methods to connect the PV cells in a module, e.g. laser cutting of the conductive or active layers
• CPC Class Codes: H01L 31/0465 comprising particular structures for the electrical interconnection of adjacent PV cells in the module H01L31/0463 takes precedence
• CPC Class Codes: H01L 31/077 the devices comprising monocrystalline or polycrystalline materials
• CPC Class Codes: H01L 31/1824 Special manufacturing methods for microcrystalline Si, uc-Si
• CPC Class Codes: Y02E 10/545 Microcrystalline silicon PV cells
• CPC Class Codes: Y02E 10/547 Monocrystalline silicon PV cells
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

Provided is a technique for manufacturing a photoelectric conversion element using a dense crystalline semiconductor film without a cavity between crystal grains. A method of manufacturing a photoelectric conversion device having a first electrode, a unit cell, and a second electrode over a substrate includes the steps of: forming a plasma region between a first electrode and a second electrode by supplying high-frequency power of 60 MHz or less to the first electrode under a condition where a pressure of a reactive gas in a chamber of a plasma CVD apparatus is set to from 450 Pa to 13332 Pa, and a distance between the first electrode and the second electrode of the plasma CVD apparatus is set to from 1 mm to 20 mm, preferably, 4 mm to 16 mm; forming deposition precursors including a crystalline semiconductor in a gas phase including the plasma region; forming a crystal nucleus having a grain size of from 5 nm to 15 nm by depositing the deposition precursors; and forming a semiconductor film having a first conductivity type, a semiconductor film effective in photoelectric conversion, or a semiconductor film having a first conductivity type in the unit cell, by growing a crystal from the crystal nucleus.

Claims

1. A method of manufacturing a photoelectric conversion device comprising a first electrode, a unit cell, and a second electrode over a substrate, comprising the steps of:

forming a plasma region between an upper electrode and a lower electrode by supplying high-frequency power of 60 MHz or less to the upper electrode under a condition where a pressure of a reactive gas in a reaction chamber of a plasma CVD apparatus is set to greater than or equal to 450 Pa and less than or equal to 13332 Pa and a distance between the upper electrode and the lower electrode of the plasma CVD apparatus is set to greater than or equal to 1 mm and less than or equal to 20 mm;

forming crystalline deposition precursors in a gas phase including the plasma region;

forming a crystal nucleus of greater than or equal to 5 nm and less than or equal to 15 nm by depositing the crystalline deposition precursors over the substrate; and

forming at least one of a first semiconductor film, a second semiconductor film and a third semiconductor film in the unit cell, by growing a crystal from the crystal nucleus,

wherein a first conductive type of the first semiconductor film and a second conductive type of the third semiconductor film are different from each other.

2. The method of manufacturing the photoelectric conversion device, according to claim 1, wherein a rare gas is introduced to the reaction chamber with the reactive gas.

3. A method of manufacturing a photoelectric conversion device comprising a first electrode, a plurality of unit cells, and a second electrode over a substrate, comprising the steps of:

forming a plasma region between an upper electrode and a lower electrode by supplying high-frequency power of 60 MHz or less to the upper electrode under a condition where a pressure of a reactive gas in a reaction chamber of a plasma CVD apparatus is set to greater than or equal to 450 Pa and less than or equal to 13332 Pa and a distance between the upper electrode and the lower electrode of the plasma CVD apparatus is set to greater than or equal to 1 mm and less than or equal to 20 mm;

forming crystalline deposition precursors in a gas phase including the plasma region;

forming a crystal nucleus of greater than or equal to 5 nm and less than or equal to 15 nm by depositing the crystalline deposition precursors over the substrate; and

forming at least one of a first semiconductor film, a second semiconductor film and a third semiconductor film in the plurality of unit cells, by growing a crystal from the crystal nucleus,

wherein a first conductive type of the first semiconductor film and a second conductive type of the third semiconductor film are different from each other.

4. The method of manufacturing the photoelectric conversion device, according to claim 3, wherein a rare gas is introduced to the reaction chamber with the reactive gas.

5. A method of manufacturing a photoelectric conversion device comprising a first electrode, a unit cell, and a second electrode over a substrate, comprising the steps of:

introducing a reactive gas into a reaction chamber of a plasma CVD apparatus through a gas supply port of an upper electrode with a plurality of projected portions, being opposite to a lower electrode;

setting a pressure of the reaction chamber to greater than or equal to 450 Pa and less than or equal to 13332 Pa;

setting a distance between the upper electrode and the lower electrode to greater than or equal to 1 mm and less than or equal to 20 mm;

forming a plasma region between the upper electrode and the lower electrode by supplying high-frequency power of 60 MHz or less to the upper electrode;

forming crystalline deposition precursors including a semiconductor in a gas phase including the plasma region;

forming a crystal nucleus of greater than or equal to 5 nm and less than or equal to 15 nm by depositing the crystalline deposition precursors over the substrate; and

forming at least one of a first semiconductor film, a second semiconductor film and a third semiconductor film in the unit cell, by growing a crystal from the crystal nucleus,

wherein a first conductive type of the first semiconductor film and a second conductive type of the third semiconductor film are different from each other.

6. The method of manufacturing the photoelectric conversion device, according to claim 5, wherein a rare gas is introduced to the reaction chamber with the reactive gas.

7. The method of manufacturing the photoelectric conversion device, according to claim 5, wherein the gas supply port is provided between each two of the plurality of projected portions.

8. The method of manufacturing the photoelectric conversion device, according to claim 5, wherein the gas supply port is provided on each of apexes of the plurality of projected portions.

9. A method of manufacturing a photoelectric conversion device comprising a first electrode, a plurality of unit cells, and a second electrode over a substrate, comprising the steps of:

introducing a reactive gas into a reaction chamber of a plasma CVD apparatus through a gas supply port of an upper electrode with a plurality of projected portions, being opposite to a lower electrode;

setting a pressure of the reaction chamber to greater than or equal to 450 Pa and less than or equal to 13332 Pa;

setting a distance between the upper electrode and the lower electrode to greater than or equal to 1 mm and less than or equal to 20 mm;

forming a plasma region between the upper electrode and the lower electrode by supplying high-frequency power of 60 MHz or less to the upper electrode;

forming crystalline deposition precursors including a semiconductor in a gas phase including the plasma region;

forming a crystal nucleus of greater than or equal to 5 nm and less than or equal to 15 nm by depositing the crystalline deposition precursors over the substrate; and

forming at least one of a first semiconductor film, a second semiconductor film and a third semiconductor film in the plurality of unit cells, by growing a crystal from the crystal nucleus,

wherein a first conductive type of the first semiconductor film and a second conductive type of the third semiconductor film are different from each other.

10. The method of manufacturing the photoelectric conversion device, according to claim 9, wherein a rare gas is introduced to the reaction chamber with the reactive gas.

11. The method of manufacturing the photoelectric conversion device, according to claim 9, wherein the gas supply port is provided between each two of the plurality of projected portions.

12. The method of manufacturing the photoelectric conversion device, according to claim 9, wherein the gas supply port is provided on each of apexes of the plurality of projected portions.

13. A method of manufacturing a photoelectric conversion device comprising a first electrode, a unit cell, and a second electrode over a substrate, the method using a plasma CVD apparatus provided with an upper electrode and a lower electrode in a reaction chamber and comprising the steps of:

introducing a reactive gas into the reaction chamber;

setting a pressure of the reaction chamber to greater than or equal to 450 Pa and less than or equal to 13332 Pa;

forming a plasma region between the upper electrode and the lower electrode by supplying high-frequency power of 60 MHz or less to the upper electrode;

forming crystalline deposition precursors in a gas phase including the plasma region;

forming a crystal nucleus of greater than or equal to 5 nm and less than or equal to 15 nm by depositing the crystalline deposition precursors; and

forming at least one of a first semiconductor film, a second semiconductor film and a third semiconductor film in the unit cell, by growing a crystal from the crystal nucleus,

wherein a first conductive type of the first semiconductor film and a second conductive type of the third semiconductor film are different from each other,

wherein the upper electrode comprises;

a plurality of projected portions for forming the plasma in the reaction chamber by supplying the high-frequency power;

a first gas supply port provided on each of apexes of the plurality of projected portions; and

a second gas supply port provided between each two of the plurality of projected portions,

the plurality of projected portions each having a tapered shape and being chamfered, and

wherein a distance between the upper electrode and the lower electrode is greater than or equal to 1 mm and less than or equal to 20 mm.

14. The method of manufacturing the photoelectric conversion device, according to claim 13, wherein a rare gas is introduced to the reaction chamber with the reactive gas.

15. A method of manufacturing a photoelectric conversion device comprising a first electrode, a plurality of unit cells, and a second electrode over a substrate, the method using a plasma CVD apparatus provided with an upper electrode and a lower electrode in a reaction chamber and comprising the steps of:

introducing a reactive gas into the reaction chamber;

setting a pressure of the reaction chamber to greater than or equal to 450 Pa and less than or equal to 13332 Pa;

forming a plasma region between the upper electrode and the lower electrode by supplying high-frequency power of 60 MHz or less to the upper electrode;

forming crystalline deposition precursors in a gas phase including the plasma region;

forming a crystal nucleus of greater than or equal to 5 nm and less than or equal to 15 nm by depositing the crystalline deposition precursors; and

forming at least one of a first semiconductor film, a second semiconductor film and a third semiconductor film in the plurality of unit cells, by growing a crystal from the crystal nucleus,

wherein a first conductive type of the first semiconductor film and a second conductive type of the third semiconductor film are different from each other,

wherein the upper electrode comprises;

a plurality of projected portions for forming the plasma in the reaction chamber by supplying the high-frequency power;

a first gas supply port provided on each of apexes of the plurality of projected portions; and

a second gas supply port provided between each two of the plurality of projected portions,

the plurality of projected portions each having a tapered shape and being chamfered, and

wherein a distance between the upper electrode and the lower electrode is greater than or equal to 1 mm and less than or equal to 20 mm.

16. The method of manufacturing the photoelectric conversion device, according to claim 15, wherein a rare gas is introduced to the reaction chamber with the reactive gas.