Methods of using selective optical excitation in deposition processes and the detection of new compositions

• US 4,637,938 A
• Filed: 08/19/1983
• Issued: 01/20/1987
• Est. Priority Date: 08/19/1983
• Status: Expired due to Term

• Current Assignee: United Solar Systems Corp.
• Original Assignee: Energy Conversion Devices
• Inventors: Lee, Henry, deNeufville, John P., Ovshinsky, Stanford R.
• Primary Examiner(s): Lusignan, Michael R.
• Application Number:
  US06/524,923
• Time in Patent Office: 1,250 Days
• Field of Search: 427/34, 427/53.1, 427/8, 427/86, 436/35, 436/172, 204/192 S, 204/192 P, 136/258, 430/128, 252/372
• US Class Current: 427/8
• CPC Class Codes: B01J 12/002 carried out in the plasma state generating or handling plasma H05H1/00
• CPC Class Codes: B01J 19/121 Coherent waves, e.g. laser beams lasers per se H01S3/00
• CPC Class Codes: C01B 33/107 Halogenated silanes
• CPC Class Codes: C01G 17/04 Halides of germanium
• CPC Class Codes: C23C 16/24 Deposition of silicon only
• CPC Class Codes: C23C 16/483 using coherent light, UV to IR, e.g. lasers
• CPC Class Codes: C23C 16/488 Protection of windows for introduction of radiation into the coating chamber
• CPC Class Codes: C23C 16/52 Controlling or regulating the coating process C23C16/45557, C23C16/279 take precedence
• CPC Class Codes: G01N 21/6402 Atomic fluorescence; Laser induced fluorescence

Abstract

The present invention generally relates to the use of fluorescence signals obtained by selective optical excitation to detect and monitor a species present during a flow reaction or decomposition of various reactants. These reactions were analyzed in situ using a tunable laser as a selective excitation source in combination with a reactor inducing such reactions with a diffusion flame or a plasma. The resultant spectra and analysis presented herein demonstrates the detection of new compositions like SiHF in the gas phase. The invention allows for pinpoint spatial probing of the reactor without perturbing the reaction. Thus, a deposition process can be controlled by monitoring a selected species and adjusting the deposition reaction parameters in response to the species'"'"' mere detection or relative concentration. The invention also contemplates perturbing deposition reactions by selectively exciting a species present in the deposition reaction to modify the deposited material so that the quality of the deposited material improves. Specifically, improved photovoltaic devices which include photoconductive material made in accordance with the present invention are disclosed herein.

Claims

1. A method of detecting a species which is a product of a chemical flow reaction occurring in a plasma, the method comprising the steps of:

generating a plasma to initiate a chemical flow reaction between at least two reactants producing a species having at least one electronically excited state;

inducing the fluorescence of said species with a laser in said plasma without perturbing said flow reaction;

measuring the fluorescence of said species in situ.

2. A method as defined in claim 1, wherein said species contains either silicon or germanium atoms.

3. A method as defined in claim 1, wherein said species is selected from the group consisting of SiH₂, SiH, SiHF, SiF, SiF₂, GeH₂, GeH, GeHF, GeF, and GeF₂.

4. A method as defined in claim 1, wherein said flow reaction includes at least one of the reactants selected from the group consisting of SiH₄, SiH₃ F, SiH₂ F₂, SiHF₃, SiF₄, GeH₄, GeH₃ F, GeH₂ F₂, GeHF₃, and GeF₄.

5. A method as defined in claim 4, wherein said flow reaction further includes hydrogen.

6. A method of detecting a species which is a product of a chemical flow reaction occurring in a diffusion flame, the method comprising the steps of:

generating a diffusion flame to initiate a chemical flow reaction between at least two reactants producing a species having at least one electronically excited state;

including the fluorescence of said species with a laser in a diffusion flame without perturbing said flow reaction;

measuring the fluorescence of said species in situ.

7. A method as defined in claim 6, wherein said species contains either silicon or germanium atoms.

8. A method as defined in claim 6, wherein said species is selected from the group consisting of SiH₂, SiH, SiHF, SiF, SiF₂, GeH₂, GeH, GeHF, GeF, and GeF₂.

9. A method as defined in claim 6, wherein said flow reaction includes a mixture of fluorine or a fluorine containing compound with at least one of the following species SiH₄, SiH₃ F, SiH₂ F₂, GeH₄, GeH₃ F, and GeH₂ F₂.

10. A method of depositing a semiconductor material on a substrate comprising the steps of:

generating a deposition reaction having a species which is a product of a chemical flow reaction using either a diffusion flame or plasma, said deposition reaction in operative contact with a substrate so that the product of said deposition reaction is a body of material deposited on said substrate;

perturbing said deposition reaction in situ by exciting an effective concentration of said species to an electronically excited state so that the deposited semiconductor material is modified, said species being a precursor to the deposited semiconductor film; and

depositing said material on said substrate.

11. A method as defined in claim 10, wherein said method further comprises controlling said deposition reaction of said generating step in response to the relative concentration of said species.

12. A method as defined in claim 10, wherein said excitation is laser induced.

13. A method as defined in claim 10, wherein said depositing step includes perturbing said deposition reaction by exciting an effective concentration of said species to a stable excited state so that the deposited material is modified.

21. The method as defined in claim 10 wherein said species is selected from the group consisting of SiH₂, SiH₄, SiHF, SiF, SiF₂, GeH, GeF and GeF₂ and said frequency for highest optical absorption is, respectively:

SiH₂, 579.7 nanometers;

SiH₄, 414.2 nanometers;

SiHF, 430 nanometers;

SiF, 436.8 nanometers;

SiF₂, 380 nanometers;

GeH, 389.8 nanometers;

GeF, 431.1 nanometers; and

GeF₂, 325.6 nanometers.

22. The method as defined in claim 12 wherein the frequency of said laser excitation corresponds to the frequency where the optical absorption for said species is the highest.

14. A method of depositing a photoconductive film comprising the steps of:

generating a chemical dissociation deposition reaction between at least two reactants using either a diffusion flame or plasma, said deposition reaction in operative contact with a substrate so that the product of said deposition reaction is a photoconductive film deposited on said substrate;

detecting a transient species having an electronically excited state by inducing the fluorescence of said species with an optical excitation source and monitoring and correlating in situ the relative concentration of said species with the quality of said photoconductive film; and

depositing said photoconductive film on said substrate.

15. A method as defined in claim 14, wherein said species is selected from the group consisting of SiH₂, SiH, SiHF, SiF, SiF₂, GeH, GeH₂, GeHF, GeF, and GeF₂.

16. A method as defined in claim 14, wherein said reactant includes at least one of the reactants selected from the group consisting of SiH₄, SiH₃ F, SiH₂ F₂, SiHF₃, SiF₄, GeH₄, GeH₃ F, GeH₂ F₂, GeHF₃, and GeF₄.

17. A method as defined in claim 14, wherein said reactant is a mixture of fluorine or a fluorine containing compound with at least one of the following species SiH₄, SiH₃ F, SiH₂ F₂, GeH₄, GeH₃ F, and GeH₂ F₂.

18. A method as defined in claim 14, wherein said method further comprises controlling said deposition reaction of said inducing step in response to the relative concentration of said species.

19. A method as defined in claim 14, wherein said depositing step further includes perturbing the deposition reaction by exciting an effective concentration of said species to a stable excited state so that the deposited photoconductive film is modified.

20. A method as defined in claim 14, wherein said optical excitation source is a laser.

23. The method as defined in claim 20 wherein the frequency of said laser excitation corresponds to the frequency where the optical absorption for said species is the highest.

24. The method as defined in claim 23, wherein said species is selected from the group consisting of SiH₂, SiH₄, SiHF, SiF, SiF₂, GeH, GeF, and GeF₂ and said frequency for highest optical absorption is, respectively, SiH₂, 579.7 nanometers;

SiH₄, 414.1 nanometers;

SiHF, 430 nanometers;

SiF, 436.8 nanometers;

SiF₂, 380 nanometers, GeH, 389.8 nanometers;

GeF, 431.1 nanometers; and

GeF₂, 325.6 nanometers.