Abstract

We describe a simple spectrometer for sensitive trace gas detection in the atmosphere. A communication laser diode is used as a light source, and a commercial integrating sphere is used as a multipass absorption cell. We developed a theoretical formulation of the relative absorption of the optical power by trace gases in the sphere and applied it to two kinds of experimental result: one that is concerned with a structureless broad absorption band of butane with the use of a 1.2-μm multimode laser diode, and one that is related to the study of an isolated and sharp rovibrational line of water vapor in air at atmospheric pressure with the use of an 830-nm single-mode laser diode. With equivalent path lengths of several meters obtained with a 10-cm-i.d. integrating sphere we can demonstrate the usefulness of such a device as a broadband multipass cell for the measurement of small absorptions.

© 1996 Optical Society of America

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  1. T. J. Johnson, F. G. Wienhold, J. P. Burrows, G. W. Harris, “Frequency modulation spectroscopy at 1.3 μm using InGaAsP lasers: a prototype field instrument for atmospheric chemistry research,” Appl. Opt. 30, 407–413 (1991).
  2. A. C. Stanton, J. A. Silver, “Measurements in the HCl 3–0 band using a near-IR InGaAsP diode laser,” Appl. Opt. 24, 5009–5015 (1988).
  3. D. E. Cooper, R. U. Martinelli, C. B. Carlisle, H. Riris, D. B. Bour, R. J. Menna, “Measurement of 12CO2:13CO2 ratios for medical diagnostics with 1.6-μm distributed-feedback semiconductor diode lasers,” Appl. Opt. 32, 6727–6731 (1993).
  4. H. C. Sun, E. A. Whittaker, “Novel étalon fringe rejection technique for laser absorption spectroscopy,” Appl. Opt. 31, 4998–5002 (1992).
  5. P. Elterman, “Integrating cavity spectroscopy,” Appl. Opt. 9, 2140–2142 (1970).
  6. A. M. Emel’yanov, V. I. Kosyakov, B. V. Makushkin, “The use of an integrating cavity for measuring small optical absorptions,” Sov. J. Opt. Technol. 45, 31–33 (1978).
  7. E. S. Fry, G. W. Kattawar, “Measurement of the absorption coefficient of ocean water using isotropic illumination,” in Ocean Optics IX, M. A. Blizard, ed., Proc. SPIE 925, 142–148 (1988).
  8. E. S. Fry, G. W. Kattawar, R. M. Pope, “Integrating cavity absorption meter,” Appl. Opt. 31, 2055–2065 (1992).
  9. E. Berger, D. W. T. Griffith, G. Schuster, S. R. Wilson, “Spectroscopy of matrices and thin films with an integrating sphere,” Appl. Spectrosc. 43, 320–324 (1989).
  10. J. A. Jacquez, H. F. Kuppenheim, “Theory of the integrating sphere,” J. Opt. Soc. Am. 45, 460–470 (1955).
  11. R. S. Longhurst, Geometrical and Physical Optics (Wiley, New York, 1967), pp. 406–428.
  12. Labsphere, Inc., A Guide to Integrating Sphere. Photometry & Radiometry and A Guide to Reflectance Materials and Coatings (Labsphere, Inc., North Sutton, N.H., 1994).
  13. J. A. Silver, “Frequency-modulation spectroscopy for trace species detection: theory and comparison among experimental methods,” Appl. Opt. 31, 707–717 (1992), and references therein.
  14. F. S. Pavone, M. Inguscio, “Frequency- and wavelength-modulation spectroscopies: comparison of experimental methods using an AlGaAs diode laser,” Appl. Phys. B 56, 118–122 (1993).
  15. M. Vervloet, Laboratoire de Photophysique Moleculaire, Universite de Paris Sud, 91405 Orsay, France (personal communication, 1994).
  16. L. S. Rothman, R. R. Gamache, R. H. Tipping, C. P. Rinsland, M. A. H. Smith, D. C. Benner, V. M. Devi, J. M. Flaud, C. Camy-Peyret, A. Perrin, A. Goldman, S. T. Masie, L. R. Brown, R. A. Toth, “The HITRAN molecular database: editions of 1991 and 1992,” J. Quant. Spectrosc. Radiat. Transfer 48, 469–507 (1993).
  17. G. Meijer, M. G. H. Boogaarts, R. T. Jongma, D. H. Parker, A. M. Wodtke, “Coherent cavity ring down spectroscopy,” Chem. Phys. Lett. 217, 112–116 (1994).

1994

G. Meijer, M. G. H. Boogaarts, R. T. Jongma, D. H. Parker, A. M. Wodtke, “Coherent cavity ring down spectroscopy,” Chem. Phys. Lett. 217, 112–116 (1994).

1993

F. S. Pavone, M. Inguscio, “Frequency- and wavelength-modulation spectroscopies: comparison of experimental methods using an AlGaAs diode laser,” Appl. Phys. B 56, 118–122 (1993).

L. S. Rothman, R. R. Gamache, R. H. Tipping, C. P. Rinsland, M. A. H. Smith, D. C. Benner, V. M. Devi, J. M. Flaud, C. Camy-Peyret, A. Perrin, A. Goldman, S. T. Masie, L. R. Brown, R. A. Toth, “The HITRAN molecular database: editions of 1991 and 1992,” J. Quant. Spectrosc. Radiat. Transfer 48, 469–507 (1993).

D. E. Cooper, R. U. Martinelli, C. B. Carlisle, H. Riris, D. B. Bour, R. J. Menna, “Measurement of 12CO2:13CO2 ratios for medical diagnostics with 1.6-μm distributed-feedback semiconductor diode lasers,” Appl. Opt. 32, 6727–6731 (1993).

1992

1991

1989

1988

A. C. Stanton, J. A. Silver, “Measurements in the HCl 3–0 band using a near-IR InGaAsP diode laser,” Appl. Opt. 24, 5009–5015 (1988).

1978

A. M. Emel’yanov, V. I. Kosyakov, B. V. Makushkin, “The use of an integrating cavity for measuring small optical absorptions,” Sov. J. Opt. Technol. 45, 31–33 (1978).

1970

1955

Benner, D. C.

L. S. Rothman, R. R. Gamache, R. H. Tipping, C. P. Rinsland, M. A. H. Smith, D. C. Benner, V. M. Devi, J. M. Flaud, C. Camy-Peyret, A. Perrin, A. Goldman, S. T. Masie, L. R. Brown, R. A. Toth, “The HITRAN molecular database: editions of 1991 and 1992,” J. Quant. Spectrosc. Radiat. Transfer 48, 469–507 (1993).

Berger, E.

Boogaarts, M. G. H.

G. Meijer, M. G. H. Boogaarts, R. T. Jongma, D. H. Parker, A. M. Wodtke, “Coherent cavity ring down spectroscopy,” Chem. Phys. Lett. 217, 112–116 (1994).

Bour, D. B.

Brown, L. R.

L. S. Rothman, R. R. Gamache, R. H. Tipping, C. P. Rinsland, M. A. H. Smith, D. C. Benner, V. M. Devi, J. M. Flaud, C. Camy-Peyret, A. Perrin, A. Goldman, S. T. Masie, L. R. Brown, R. A. Toth, “The HITRAN molecular database: editions of 1991 and 1992,” J. Quant. Spectrosc. Radiat. Transfer 48, 469–507 (1993).

Burrows, J. P.

Camy-Peyret, C.

L. S. Rothman, R. R. Gamache, R. H. Tipping, C. P. Rinsland, M. A. H. Smith, D. C. Benner, V. M. Devi, J. M. Flaud, C. Camy-Peyret, A. Perrin, A. Goldman, S. T. Masie, L. R. Brown, R. A. Toth, “The HITRAN molecular database: editions of 1991 and 1992,” J. Quant. Spectrosc. Radiat. Transfer 48, 469–507 (1993).

Carlisle, C. B.

Cooper, D. E.

Devi, V. M.

L. S. Rothman, R. R. Gamache, R. H. Tipping, C. P. Rinsland, M. A. H. Smith, D. C. Benner, V. M. Devi, J. M. Flaud, C. Camy-Peyret, A. Perrin, A. Goldman, S. T. Masie, L. R. Brown, R. A. Toth, “The HITRAN molecular database: editions of 1991 and 1992,” J. Quant. Spectrosc. Radiat. Transfer 48, 469–507 (1993).

Elterman, P.

Emel’yanov, A. M.

A. M. Emel’yanov, V. I. Kosyakov, B. V. Makushkin, “The use of an integrating cavity for measuring small optical absorptions,” Sov. J. Opt. Technol. 45, 31–33 (1978).

Flaud, J. M.

L. S. Rothman, R. R. Gamache, R. H. Tipping, C. P. Rinsland, M. A. H. Smith, D. C. Benner, V. M. Devi, J. M. Flaud, C. Camy-Peyret, A. Perrin, A. Goldman, S. T. Masie, L. R. Brown, R. A. Toth, “The HITRAN molecular database: editions of 1991 and 1992,” J. Quant. Spectrosc. Radiat. Transfer 48, 469–507 (1993).

Fry, E. S.

E. S. Fry, G. W. Kattawar, R. M. Pope, “Integrating cavity absorption meter,” Appl. Opt. 31, 2055–2065 (1992).

E. S. Fry, G. W. Kattawar, “Measurement of the absorption coefficient of ocean water using isotropic illumination,” in Ocean Optics IX, M. A. Blizard, ed., Proc. SPIE 925, 142–148 (1988).

Gamache, R. R.

L. S. Rothman, R. R. Gamache, R. H. Tipping, C. P. Rinsland, M. A. H. Smith, D. C. Benner, V. M. Devi, J. M. Flaud, C. Camy-Peyret, A. Perrin, A. Goldman, S. T. Masie, L. R. Brown, R. A. Toth, “The HITRAN molecular database: editions of 1991 and 1992,” J. Quant. Spectrosc. Radiat. Transfer 48, 469–507 (1993).

Goldman, A.

L. S. Rothman, R. R. Gamache, R. H. Tipping, C. P. Rinsland, M. A. H. Smith, D. C. Benner, V. M. Devi, J. M. Flaud, C. Camy-Peyret, A. Perrin, A. Goldman, S. T. Masie, L. R. Brown, R. A. Toth, “The HITRAN molecular database: editions of 1991 and 1992,” J. Quant. Spectrosc. Radiat. Transfer 48, 469–507 (1993).

Griffith, D. W. T.

Harris, G. W.

Inguscio, M.

F. S. Pavone, M. Inguscio, “Frequency- and wavelength-modulation spectroscopies: comparison of experimental methods using an AlGaAs diode laser,” Appl. Phys. B 56, 118–122 (1993).

Jacquez, J. A.

Johnson, T. J.

Jongma, R. T.

G. Meijer, M. G. H. Boogaarts, R. T. Jongma, D. H. Parker, A. M. Wodtke, “Coherent cavity ring down spectroscopy,” Chem. Phys. Lett. 217, 112–116 (1994).

Kattawar, G. W.

E. S. Fry, G. W. Kattawar, R. M. Pope, “Integrating cavity absorption meter,” Appl. Opt. 31, 2055–2065 (1992).

E. S. Fry, G. W. Kattawar, “Measurement of the absorption coefficient of ocean water using isotropic illumination,” in Ocean Optics IX, M. A. Blizard, ed., Proc. SPIE 925, 142–148 (1988).

Kosyakov, V. I.

A. M. Emel’yanov, V. I. Kosyakov, B. V. Makushkin, “The use of an integrating cavity for measuring small optical absorptions,” Sov. J. Opt. Technol. 45, 31–33 (1978).

Kuppenheim, H. F.

Longhurst, R. S.

R. S. Longhurst, Geometrical and Physical Optics (Wiley, New York, 1967), pp. 406–428.

Makushkin, B. V.

A. M. Emel’yanov, V. I. Kosyakov, B. V. Makushkin, “The use of an integrating cavity for measuring small optical absorptions,” Sov. J. Opt. Technol. 45, 31–33 (1978).

Martinelli, R. U.

Masie, S. T.

L. S. Rothman, R. R. Gamache, R. H. Tipping, C. P. Rinsland, M. A. H. Smith, D. C. Benner, V. M. Devi, J. M. Flaud, C. Camy-Peyret, A. Perrin, A. Goldman, S. T. Masie, L. R. Brown, R. A. Toth, “The HITRAN molecular database: editions of 1991 and 1992,” J. Quant. Spectrosc. Radiat. Transfer 48, 469–507 (1993).

Meijer, G.

G. Meijer, M. G. H. Boogaarts, R. T. Jongma, D. H. Parker, A. M. Wodtke, “Coherent cavity ring down spectroscopy,” Chem. Phys. Lett. 217, 112–116 (1994).

Menna, R. J.

Parker, D. H.

G. Meijer, M. G. H. Boogaarts, R. T. Jongma, D. H. Parker, A. M. Wodtke, “Coherent cavity ring down spectroscopy,” Chem. Phys. Lett. 217, 112–116 (1994).

Pavone, F. S.

F. S. Pavone, M. Inguscio, “Frequency- and wavelength-modulation spectroscopies: comparison of experimental methods using an AlGaAs diode laser,” Appl. Phys. B 56, 118–122 (1993).

Perrin, A.

L. S. Rothman, R. R. Gamache, R. H. Tipping, C. P. Rinsland, M. A. H. Smith, D. C. Benner, V. M. Devi, J. M. Flaud, C. Camy-Peyret, A. Perrin, A. Goldman, S. T. Masie, L. R. Brown, R. A. Toth, “The HITRAN molecular database: editions of 1991 and 1992,” J. Quant. Spectrosc. Radiat. Transfer 48, 469–507 (1993).

Pope, R. M.

Rinsland, C. P.

L. S. Rothman, R. R. Gamache, R. H. Tipping, C. P. Rinsland, M. A. H. Smith, D. C. Benner, V. M. Devi, J. M. Flaud, C. Camy-Peyret, A. Perrin, A. Goldman, S. T. Masie, L. R. Brown, R. A. Toth, “The HITRAN molecular database: editions of 1991 and 1992,” J. Quant. Spectrosc. Radiat. Transfer 48, 469–507 (1993).

Riris, H.

Rothman, L. S.

L. S. Rothman, R. R. Gamache, R. H. Tipping, C. P. Rinsland, M. A. H. Smith, D. C. Benner, V. M. Devi, J. M. Flaud, C. Camy-Peyret, A. Perrin, A. Goldman, S. T. Masie, L. R. Brown, R. A. Toth, “The HITRAN molecular database: editions of 1991 and 1992,” J. Quant. Spectrosc. Radiat. Transfer 48, 469–507 (1993).

Schuster, G.

Silver, J. A.

J. A. Silver, “Frequency-modulation spectroscopy for trace species detection: theory and comparison among experimental methods,” Appl. Opt. 31, 707–717 (1992), and references therein.

A. C. Stanton, J. A. Silver, “Measurements in the HCl 3–0 band using a near-IR InGaAsP diode laser,” Appl. Opt. 24, 5009–5015 (1988).

Smith, M. A. H.

L. S. Rothman, R. R. Gamache, R. H. Tipping, C. P. Rinsland, M. A. H. Smith, D. C. Benner, V. M. Devi, J. M. Flaud, C. Camy-Peyret, A. Perrin, A. Goldman, S. T. Masie, L. R. Brown, R. A. Toth, “The HITRAN molecular database: editions of 1991 and 1992,” J. Quant. Spectrosc. Radiat. Transfer 48, 469–507 (1993).

Stanton, A. C.

A. C. Stanton, J. A. Silver, “Measurements in the HCl 3–0 band using a near-IR InGaAsP diode laser,” Appl. Opt. 24, 5009–5015 (1988).

Sun, H. C.

Tipping, R. H.

L. S. Rothman, R. R. Gamache, R. H. Tipping, C. P. Rinsland, M. A. H. Smith, D. C. Benner, V. M. Devi, J. M. Flaud, C. Camy-Peyret, A. Perrin, A. Goldman, S. T. Masie, L. R. Brown, R. A. Toth, “The HITRAN molecular database: editions of 1991 and 1992,” J. Quant. Spectrosc. Radiat. Transfer 48, 469–507 (1993).

Toth, R. A.

L. S. Rothman, R. R. Gamache, R. H. Tipping, C. P. Rinsland, M. A. H. Smith, D. C. Benner, V. M. Devi, J. M. Flaud, C. Camy-Peyret, A. Perrin, A. Goldman, S. T. Masie, L. R. Brown, R. A. Toth, “The HITRAN molecular database: editions of 1991 and 1992,” J. Quant. Spectrosc. Radiat. Transfer 48, 469–507 (1993).

Vervloet, M.

M. Vervloet, Laboratoire de Photophysique Moleculaire, Universite de Paris Sud, 91405 Orsay, France (personal communication, 1994).

Whittaker, E. A.

Wienhold, F. G.

Wilson, S. R.

Wodtke, A. M.

G. Meijer, M. G. H. Boogaarts, R. T. Jongma, D. H. Parker, A. M. Wodtke, “Coherent cavity ring down spectroscopy,” Chem. Phys. Lett. 217, 112–116 (1994).

Appl. Opt.

Appl. Phys. B

F. S. Pavone, M. Inguscio, “Frequency- and wavelength-modulation spectroscopies: comparison of experimental methods using an AlGaAs diode laser,” Appl. Phys. B 56, 118–122 (1993).

Appl. Spectrosc.

Chem. Phys. Lett.

G. Meijer, M. G. H. Boogaarts, R. T. Jongma, D. H. Parker, A. M. Wodtke, “Coherent cavity ring down spectroscopy,” Chem. Phys. Lett. 217, 112–116 (1994).

J. Opt. Soc. Am.

J. Quant. Spectrosc. Radiat. Transfer

L. S. Rothman, R. R. Gamache, R. H. Tipping, C. P. Rinsland, M. A. H. Smith, D. C. Benner, V. M. Devi, J. M. Flaud, C. Camy-Peyret, A. Perrin, A. Goldman, S. T. Masie, L. R. Brown, R. A. Toth, “The HITRAN molecular database: editions of 1991 and 1992,” J. Quant. Spectrosc. Radiat. Transfer 48, 469–507 (1993).

Sov. J. Opt. Technol.

A. M. Emel’yanov, V. I. Kosyakov, B. V. Makushkin, “The use of an integrating cavity for measuring small optical absorptions,” Sov. J. Opt. Technol. 45, 31–33 (1978).

Other

E. S. Fry, G. W. Kattawar, “Measurement of the absorption coefficient of ocean water using isotropic illumination,” in Ocean Optics IX, M. A. Blizard, ed., Proc. SPIE 925, 142–148 (1988).

R. S. Longhurst, Geometrical and Physical Optics (Wiley, New York, 1967), pp. 406–428.

Labsphere, Inc., A Guide to Integrating Sphere. Photometry & Radiometry and A Guide to Reflectance Materials and Coatings (Labsphere, Inc., North Sutton, N.H., 1994).

M. Vervloet, Laboratoire de Photophysique Moleculaire, Universite de Paris Sud, 91405 Orsay, France (personal communication, 1994).

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Figures (3)

Fig. 1
Fig. 1

Definition of the various symbols used in the mathematical formulation of the absorption in the integrating sphere: dS 1 and dS 2, surface elements; θ, angle between the normal of dS 1 and dS 2 and the direction dS 1–dS 2; R, radius of the sphere.

Fig. 2
Fig. 2

Schematic diagram of the experimental arrangement.

Fig. 3
Fig. 3

Recording of the 12062.409-cm−1 water vapor line obtained in the 4-in. (10-cm) integrating sphere. The absorption coefficient of the line is 2.4 × 10−5 cm−1. The scan duration is 1 s. The lock-in time constant is 10 ms.

Equations (16)

Equations on this page are rendered with MathJax. Learn more.

d 2 Φ = L d S 1 d S 2 cos 2 θ / z 2 ,
d 2 Φ = 2 π L d S 1 cos θ sin θ d θ .
d 2 Φ ( α ) = d 2 Φ exp [ - α ( ν ) z ] .
d Φ ( α ) = 2 π L d S 1 0 π / 2 exp [ - 2 R α ( ν ) cos θ ] cos θ sin θ d θ .
d Φ ( α ) = 2 π L d S 1 / [ 4 R 2 α 2 ( ν ) ] { 1 - [ 1 + 2 R α ( ν ) ] exp [ - 2 R α ( ν ) ] } ,
d Φ ( α ) = π L d S 1 [ 1 - 2 / 3 α ( ν ) D ] .
d Φ ( 0 ) = π L d S 1 ,
d Φ ( α ) = d Φ ( 0 ) [ 1 - 2 / 3 α ( ν ) D ] .
Φ ( α ) = s d Φ ( α ) = Φ ( 0 ) [ 1 - 2 / 3 α ( ν ) D ] ,
[ Φ ( 0 ) - Φ ( α ) ] / Φ ( 0 ) = α ( ν ) 2 / 3 D = α ( ν ) L eff .
Φ e ( α ) / Φ i = { ρ [ 1 - α ( ν ) L eff ] h } / × { 1 - ρ [ 1 - α ( ν ) L eff ] ( 1 - h ) } ,
Φ e ( 0 ) / Φ i = ( ρ h ) / [ 1 - ρ ( 1 - h ) ] .
Φ e ( α ) / Φ e ( 0 ) = [ 1 - α ( ν ) L eff ] [ 1 - ρ ( 1 - h ) ] / × { 1 - ρ [ 1 - α ( ν ) L eff ] ( 1 - h ) } ,
Δ Φ / Φ e ( 0 ) = [ α ( ν ) L eff ] / { 1 - ρ [ 1 - α ( ν ) L eff ] ( 1 - h ) } .
L eq = L eff / ( 1 - ρ ) = 2 / 3 D / ( 1 - ρ ) .
Δ Φ / Φ e ( 0 ) = α ( ν ) L eff / [ 1 - ρ ( 1 - h ) ] = N σ ( ν ) L eff / [ 1 - ρ ( 1 - h ) ] ,

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