Apparatus for forming thin-film heterojunction solar cells employing materials selected from the class of I-III-VI.sub.2 chalcopyrite compounds

• US 4,392,451 A
• Filed: 07/02/1981
• Issued: 07/12/1983
• Est. Priority Date: 12/31/1980
• Status: Expired due to Fees

• Current Assignee: The Boeing Co.
• Original Assignee: The Boeing Co.
• Inventors: Chen, Wen S., Mickelsen, Reid A.
• Primary Examiner(s): Smith, John D.
• Assistant Examiner(s): Plantz, Bernard F.
• Application Number:
  US06/278,343
• Time in Patent Office: 740 Days
• Field of Search: 118/688, 118/689, 118/690, 118/691, 118/712, 118/718, 118/725, 118/719, 118/730, 427/255.2, 427/255.7, 427/87, 427/255.1, 427/10
• US Class Current: 118/690
• CPC Class Codes: C23C 14/027 Graded interfaces
• CPC Class Codes: C23C 14/54 Controlling or regulating the coating process
• CPC Class Codes: H01L 31/0322 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
• CPC Class Codes: H01L 31/03365 comprising only Cu2X / CdX heterojunctions, X being an element of Group VI of the Periodic Table
• CPC Class Codes: H01L 31/072 the potential barriers being only of the PN heterojunction type
• CPC Class Codes: H01L 31/0749 including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
• CPC Class Codes: H01L 31/18 Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
• CPC Class Codes: H01L 31/1876 Particular processes or apparatus for batch treatment of the devices
• CPC Class Codes: Y02E 10/541 CuInSe2 material PV cells
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10S 148/006 Apparatus
• CPC Class Codes: Y10S 148/12 Photocathodes-Cs coated and solar cell
• CPC Class Codes: Y10S 148/169 Vacuum deposition, e.g. including molecular beam epitaxy

Abstract

Apparatus for forming thin-film, large area solar cells having a relatively high light-to-electrical energy conversion efficiency and characterized in that the cell comprises a p-n-type heterojunction formed of: (i) a first semiconductor layer comprising a photovoltaic active material selected from the class of I-III-VI₂ chalcopyrite ternary materials which is vacuum deposited in a thin "composition-graded" layer ranging from on the order of about 2.5 microns to about 5.0 microns (≅2.5 μm to ≅5.0 μm) and wherein the lower region of the photovoltaic active material preferably comprises a low resistivity region of p-type semiconductor material having a superimposed region of relatively high resistivity, transient n-type semiconductor material defining a transient p-n homojunction; and (ii), a second semiconductor layer comprising a low resistivity n-type semiconductor material wherein interdiffusion (a) between the elemental constituents of the two discrete juxtaposed regions of the first semiconductor layer defining a transient p-n homojunction layer, and (b) between the transient n-type material in the first semiconductor layer and the second n-type semiconductor layer, causes the transient n-type material in the first semiconductor layer to evolve into p-type material, thereby defining a thin layer heterojunction device characterized by the absence of voids, vacancies and nodules which tend to reduce the energy conversion efficiency of the system.

Claims

1. Apparatus for forming a photovoltaic light-to-electrical energy transducer of the type comprising a thin-film, A-B-type heterojunction formed on a substrate from a first ternary semiconductor material and a second semiconductor material, comprising, in combination:

(a) first means for forming a low-resistivity base metal contact on the substrate;

(b) second means for forming a transient A-B-type, thin-film homojunction on the base metal contact by simultaneous elemental evaporation of the constituent elements of the ternary semiconductor material, said second means including;

(i) means for monitoring the ratio of two of the constituent metallic elements of the ternary semiconductor material being evaporatively formed on the base metal contact;

(ii) means for establishing an initial ratio of the two constituent metallic elements being monitored so that the evaporation stream of elements being deposited on the base metal contact is slightly enriched by a slight excess of one metallic elemental constituent as compared to the stoichiometric condition of the ternary semiconductor material so as to permit formation of a first region of low resistivity semiconductor material on the base metal contact; and

,

(iii) means for adjusting the ratio of the two constituent elements being monitored during simultaneous elemental evaporation thereof so that the evaporative stream of elements being deposited on the first region of low resistivity semiconductor material contains a slight deficiency of the one metallic elemental constituent as compared to the stoichiometric condition of the ternary semiconductor material so as to permit formation of a second region of relatively high-resistivity transient semiconductor material on the first region of low resistivity semiconductor material, thereby forming a transient A-B-type homojunction; and

,

(c) third means for forming a low resistivity, thin-film layer of said second semiconductor material on the transient A-B-type homojunction with such layer in face-to-face contact with the second region of the transient homojunction and having a p-type or n-type state corresponding to the transient state of the high resistivity region;

so that upon elemental interdiffusion of the elemental constituents formed on the substrate by said second and third means, the second region of relatively high resistivity transient semiconductor material is permitted to evolve into a relatively high resistivity region of semiconductor material having a p-type or n-type state corresponding to the state of the first region of low resistivity semiconductor material to thereby form a thin-film, A-B-type, heterojunction.

2. Apparatus as set forth in claim 1 wherein means are provided for maintaining the substrate temperature within said apparatus at a range of about 350°

C. to 500°

C. during simultaneous elemental evaporation of the ternary semiconductor material.

3. Apparatus as set forth in claim 1 wherein means are provided for maintaining the substrate temperature within said apparatus at a temperature level on the order of 350°

C. during formation of all of the first region of low resistivity semiconductor material and a portion only of formation of the second region of high resistivity transient semiconductor material, and for thereafter increasing the temperature level during the balance of the simultaneous elemental evaporation process for the second region to on the order of 450°

C. ±

≅

25°

C. but less than 500°

C.

4. Apparatus as set forth in claims 1, 2 or 3 wherein means are provided for maintaining the pressure within said apparatus at 3-8×

10^-6 torr. during simultaneous elemental evaporation of the ternary semiconductor material.

5. Apparatus as set forth in claim 1, 2 or 3 wherein means are provided for maintaining the substrate temperature within the range of about 150°

C. to about 200°

C. during deposition of the second semiconductor material by said third means.

6. Apparatus as set forth in claims 1, 2 or 3 further characterized in that said apparatus includes a planetary-type deposition fixture having a plurality of planets, means for mounting the substrates in said planets, and means for simultaneously rotating said planets about first and second axes so as to minimize deposition nonuniformities on the substrates.

7. Apparatus as set forth in claims 1, 2 or 3 further characterized in that said apparatus comprises a continuous in-line apparatus having a plurality of serially located process zones including a first zone wherein said first means is operative to form the low-resistivity base metal contact on the substrate, a second zone wherein said second means is operative to evaporate the constituent elements of the ternary semiconductor material on the base metal contact, a third zone wherein said third means is operative to form the low-resistivity thin-film layer of said second semiconductor material on the homojunction deposited by said second means, a fourth zone including means for applying a contact grid on the thin-film layer of said second semiconductor material, and a fifth zone including means for depositing an SiO_x layer on the contact grid, and conveyor means for transporting substrates successively through said first, second, third, fourth and fifth zones.