Abstract

We designed an asymmetric Czerny-Turner-type spectrometer with a spectral resolution of approximately 1 cm-1 and a focal length of 500 mm (F/4.1) to improve the aberration properties: (1) coma aberration was corrected by use of a particular incident angle for a condensing mirror based on Shafer’s equation, (2) astigmatism was corrected by use of a toroidal condensing mirror, (3) the optimum distance was found between a grating and condensing mirror so that the centered light and marginal light at the detector possess the same incident angles to the condensing mirror (the aberration is therefore excellently corrected over the whole detector surfaces), and (4) these optimal configurations are ensured in a wide wavelength between 400 and 800 nm by use of gratings with different grooves. Then the spectrometer was constructed, and the excellent optical properties were confirmed with aligned fiber images and Raman spectra from copper phthalocyanine.

© 2002 Optical Society of America

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References

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  1. J.O’M Bockris, A. K. N. Reddy, Modern Electrochemistry (Plenum, New York, 1973).
    [CrossRef]
  2. J. Lipkowski, P. N. Ross, Adsorption of Molecules at Metal Electrodes (VCH, New York, 1992).
  3. M. Futamata, “Surface-plasmon-polariton-enhanced Raman scattering from adsorbates on ‘smooth’ metal surface: the effect of thickness and dielectric properties of constituents,” Langmuir 11, 3894–3902 (1995).
    [CrossRef]
  4. M. Futamata, “Surface-plasmon-polariton-enhanced Raman scattering from self-assembled monolayers of p-nitrothiophenol and p-aminothiophenol on silver,” J. Phys. Chem. 99, 11901–11908 (1995).
    [CrossRef]
  5. Single-photon detection is possible with the adoption of an image intensifier and a CCD detector (for instance, see catalog of IMAX-1024 from Roper Scientific, Tucson, Ariz.). However, because an electrode-solution interface contains stray light from a bulk solution, metal electrode surface, window, or prism, it is quite difficult to discriminate and detect only the Raman signal from monolayer adsorbates. Thus the Raman signal from the interface must be enhanced for this purpose as described above.
  6. H. Raether, Surface Plasmon Polariton (Springer-Verlag, Berlin, 1988).
  7. E. Burstein, F. de Martini, Polaritons (Pergamon, New York, 1974), p. 117.
  8. M. Futamata, “Coadsorbed state of uracil, water and sulfate species on the gold electrode surface,” Chem. Phys. Lett. 317, 304–309 (2000).
    [CrossRef]
  9. M. Futamata, “Adsorbed state of BiPy22+ on Au(111) electrode,” J. Phys. Chem. 105, 6933–6942 (2001).
  10. Y. Maruyama, M. Ishikawa, M. Futamata, “Single molecule detection of DNA base molecule using surface enhanced Raman scattering,” Chem. Lett.August2001, pp. 834–835.
  11. M. Futamata, A. Bruckbauer, “ATR-scanning near-field-Raman spectroscopy,” Jpn. J. Appl. Phys. 40, 4423–4429 (2001).
    [CrossRef]
  12. M. Futamata, “Dielectric filter for highly-sensitive Raman spectroscopy,” Appl. Spectrosc. 50, 199–204 (1996).
    [CrossRef]
  13. For instance, see technical notes for Spectra-Pro-150 (Acton Research Corporation, 525 Main Street, Acton, Mass. 01720), for HR-460 (Jobin Yvon S.A., 16-18 rue du Canal, 91165 Longjumeau Cedex, France; see also http://www.isainc.com/systems/theory/oos/oos.htm ) and for 250IS (Chromex), Abuquerque, N. Mex., 1995).
  14. “Chromex parallel spectroscopy,” user’s guide for Chromex spectrograph (Chromex Albuquerque, N. Mex.1995), pp. 11–13.
  15. A. Shafer, L. R. Megill, A. Droppleman, “Optimization of the Czerny-Turner spectrometer,” J. Opt. Soc. Am. 54, 879–887 (1964).
    [CrossRef]
  16. J. Reader, “Optimizing Czerny-Turner spectrographs: a comparison between analytic theory and ray tracing,” J. Opt. Soc. Am. 59, 1189–1196 (1969).
    [CrossRef]
  17. H. G. Beutler, “The theory of the concave grating,” J. Opt. Soc. Am. 35, 311–350 (1945).
    [CrossRef]
  18. W. G. Fastie, “High speed plane grating spectrograph and monochromator,” U.S. patent3,011,391 (5December1961).
  19. G. R. Rosendahl, “Contributions of the optics of mirror systems and gratings with oblique incidence. III. Some applications,” J. Opt. Soc. Am. 52, 412–415 (1962).
    [CrossRef]
  20. F. A. Jenkins, H. E. White, Fundamentals of Optics (McGraw-Hill, New York, 1950), p. 92.
  21. Rather excellent aberration properties were observed even at 550 nm with the 1200 grooves/mm grating; however, the spectral resolution with the slit width of 50 mm grows to approximately 3 cm-1. Moreover, poor aberration was obtained at 400 nm owing to the deviation from the optimum configuration.

2001 (3)

M. Futamata, “Adsorbed state of BiPy22+ on Au(111) electrode,” J. Phys. Chem. 105, 6933–6942 (2001).

Y. Maruyama, M. Ishikawa, M. Futamata, “Single molecule detection of DNA base molecule using surface enhanced Raman scattering,” Chem. Lett.August2001, pp. 834–835.

M. Futamata, A. Bruckbauer, “ATR-scanning near-field-Raman spectroscopy,” Jpn. J. Appl. Phys. 40, 4423–4429 (2001).
[CrossRef]

2000 (1)

M. Futamata, “Coadsorbed state of uracil, water and sulfate species on the gold electrode surface,” Chem. Phys. Lett. 317, 304–309 (2000).
[CrossRef]

1996 (1)

1995 (2)

M. Futamata, “Surface-plasmon-polariton-enhanced Raman scattering from adsorbates on ‘smooth’ metal surface: the effect of thickness and dielectric properties of constituents,” Langmuir 11, 3894–3902 (1995).
[CrossRef]

M. Futamata, “Surface-plasmon-polariton-enhanced Raman scattering from self-assembled monolayers of p-nitrothiophenol and p-aminothiophenol on silver,” J. Phys. Chem. 99, 11901–11908 (1995).
[CrossRef]

1969 (1)

1964 (1)

1962 (1)

1945 (1)

Beutler, H. G.

Bockris, J.O’M

J.O’M Bockris, A. K. N. Reddy, Modern Electrochemistry (Plenum, New York, 1973).
[CrossRef]

Bruckbauer, A.

M. Futamata, A. Bruckbauer, “ATR-scanning near-field-Raman spectroscopy,” Jpn. J. Appl. Phys. 40, 4423–4429 (2001).
[CrossRef]

Burstein, E.

E. Burstein, F. de Martini, Polaritons (Pergamon, New York, 1974), p. 117.

de Martini, F.

E. Burstein, F. de Martini, Polaritons (Pergamon, New York, 1974), p. 117.

Droppleman, A.

Fastie, W. G.

W. G. Fastie, “High speed plane grating spectrograph and monochromator,” U.S. patent3,011,391 (5December1961).

Futamata, M.

M. Futamata, “Adsorbed state of BiPy22+ on Au(111) electrode,” J. Phys. Chem. 105, 6933–6942 (2001).

Y. Maruyama, M. Ishikawa, M. Futamata, “Single molecule detection of DNA base molecule using surface enhanced Raman scattering,” Chem. Lett.August2001, pp. 834–835.

M. Futamata, A. Bruckbauer, “ATR-scanning near-field-Raman spectroscopy,” Jpn. J. Appl. Phys. 40, 4423–4429 (2001).
[CrossRef]

M. Futamata, “Coadsorbed state of uracil, water and sulfate species on the gold electrode surface,” Chem. Phys. Lett. 317, 304–309 (2000).
[CrossRef]

M. Futamata, “Dielectric filter for highly-sensitive Raman spectroscopy,” Appl. Spectrosc. 50, 199–204 (1996).
[CrossRef]

M. Futamata, “Surface-plasmon-polariton-enhanced Raman scattering from adsorbates on ‘smooth’ metal surface: the effect of thickness and dielectric properties of constituents,” Langmuir 11, 3894–3902 (1995).
[CrossRef]

M. Futamata, “Surface-plasmon-polariton-enhanced Raman scattering from self-assembled monolayers of p-nitrothiophenol and p-aminothiophenol on silver,” J. Phys. Chem. 99, 11901–11908 (1995).
[CrossRef]

Ishikawa, M.

Y. Maruyama, M. Ishikawa, M. Futamata, “Single molecule detection of DNA base molecule using surface enhanced Raman scattering,” Chem. Lett.August2001, pp. 834–835.

Jenkins, F. A.

F. A. Jenkins, H. E. White, Fundamentals of Optics (McGraw-Hill, New York, 1950), p. 92.

Lipkowski, J.

J. Lipkowski, P. N. Ross, Adsorption of Molecules at Metal Electrodes (VCH, New York, 1992).

Maruyama, Y.

Y. Maruyama, M. Ishikawa, M. Futamata, “Single molecule detection of DNA base molecule using surface enhanced Raman scattering,” Chem. Lett.August2001, pp. 834–835.

Megill, L. R.

Raether, H.

H. Raether, Surface Plasmon Polariton (Springer-Verlag, Berlin, 1988).

Reader, J.

Reddy, A. K. N.

J.O’M Bockris, A. K. N. Reddy, Modern Electrochemistry (Plenum, New York, 1973).
[CrossRef]

Rosendahl, G. R.

Ross, P. N.

J. Lipkowski, P. N. Ross, Adsorption of Molecules at Metal Electrodes (VCH, New York, 1992).

Shafer, A.

White, H. E.

F. A. Jenkins, H. E. White, Fundamentals of Optics (McGraw-Hill, New York, 1950), p. 92.

Appl. Spectrosc. (1)

Chem. Lett. (1)

Y. Maruyama, M. Ishikawa, M. Futamata, “Single molecule detection of DNA base molecule using surface enhanced Raman scattering,” Chem. Lett.August2001, pp. 834–835.

Chem. Phys. Lett. (1)

M. Futamata, “Coadsorbed state of uracil, water and sulfate species on the gold electrode surface,” Chem. Phys. Lett. 317, 304–309 (2000).
[CrossRef]

J. Opt. Soc. Am. (4)

J. Phys. Chem. (2)

M. Futamata, “Adsorbed state of BiPy22+ on Au(111) electrode,” J. Phys. Chem. 105, 6933–6942 (2001).

M. Futamata, “Surface-plasmon-polariton-enhanced Raman scattering from self-assembled monolayers of p-nitrothiophenol and p-aminothiophenol on silver,” J. Phys. Chem. 99, 11901–11908 (1995).
[CrossRef]

Jpn. J. Appl. Phys. (1)

M. Futamata, A. Bruckbauer, “ATR-scanning near-field-Raman spectroscopy,” Jpn. J. Appl. Phys. 40, 4423–4429 (2001).
[CrossRef]

Langmuir (1)

M. Futamata, “Surface-plasmon-polariton-enhanced Raman scattering from adsorbates on ‘smooth’ metal surface: the effect of thickness and dielectric properties of constituents,” Langmuir 11, 3894–3902 (1995).
[CrossRef]

Other (10)

F. A. Jenkins, H. E. White, Fundamentals of Optics (McGraw-Hill, New York, 1950), p. 92.

Rather excellent aberration properties were observed even at 550 nm with the 1200 grooves/mm grating; however, the spectral resolution with the slit width of 50 mm grows to approximately 3 cm-1. Moreover, poor aberration was obtained at 400 nm owing to the deviation from the optimum configuration.

For instance, see technical notes for Spectra-Pro-150 (Acton Research Corporation, 525 Main Street, Acton, Mass. 01720), for HR-460 (Jobin Yvon S.A., 16-18 rue du Canal, 91165 Longjumeau Cedex, France; see also http://www.isainc.com/systems/theory/oos/oos.htm ) and for 250IS (Chromex), Abuquerque, N. Mex., 1995).

“Chromex parallel spectroscopy,” user’s guide for Chromex spectrograph (Chromex Albuquerque, N. Mex.1995), pp. 11–13.

W. G. Fastie, “High speed plane grating spectrograph and monochromator,” U.S. patent3,011,391 (5December1961).

Single-photon detection is possible with the adoption of an image intensifier and a CCD detector (for instance, see catalog of IMAX-1024 from Roper Scientific, Tucson, Ariz.). However, because an electrode-solution interface contains stray light from a bulk solution, metal electrode surface, window, or prism, it is quite difficult to discriminate and detect only the Raman signal from monolayer adsorbates. Thus the Raman signal from the interface must be enhanced for this purpose as described above.

H. Raether, Surface Plasmon Polariton (Springer-Verlag, Berlin, 1988).

E. Burstein, F. de Martini, Polaritons (Pergamon, New York, 1974), p. 117.

J.O’M Bockris, A. K. N. Reddy, Modern Electrochemistry (Plenum, New York, 1973).
[CrossRef]

J. Lipkowski, P. N. Ross, Adsorption of Molecules at Metal Electrodes (VCH, New York, 1992).

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Figures (19)

Fig. 1
Fig. 1

Optical setup of the designed spectrometer, where ES, Mcl, G, Mpl, Mcd, and IP are the entrance slit, collimating mirror, grating, plane mirror, condensing mirror, and image plane, respectively. The figure shows the incident (i) and diffraction (γ) angles for the grating.

Fig. 2
Fig. 2

Spot diagram for a point light source placed at the entrance slit: (a) with two spherical mirrors for the collimating and the condensing mirrors and (b) with the parameters obtained from Eqs. (1) and (2) at different image positions. In Figs. 3, 6, 7, 9, and 10, the defocused positions (in micrometers) are denoted with respect to the nominal focal length of the condensing mirror at the particular angle of incidence.

Fig. 3
Fig. 3

Spot diagrams at the centered and marginal points on the detector for the optimized L g-cd = r T2 cos δ2: (a) 540 nm (left side), (b) 550 nm (center), (c) 560 nm (right side).

Fig. 4
Fig. 4

Slit images of 100 µm × 100 µm at the centered and marginal points on the detector for the optimized L g-cd = r T2 cos δ2: (a) 540 nm (left side), (b) 550 nm (center), and (c) 560 nm (right side).

Fig. 5
Fig. 5

Optical path for the centered light (550 nm) and marginal light (540 and 560 nm) in the designed spectrometer, where ES, Mcl, G, Mpl, Mcd, and IM are the entrance slit, collimating mirror, grating, plane mirror, condensing mirror, and image plane, respectively. The definition of the incident and diffraction angles at the grating are also given; here N(0) and N(1) denote the line vertical to the substrate plane and slope of the grating [see also Eqs. (1) and (2) and (5) and (6)].

Fig. 6
Fig. 6

Aberration at the centered and marginal points on the detector for different t G-C = r T2 cos δ2 + 200: (a) 540 nm (left side), (b) 550 nm (center), and (c) 560 nm (right side).

Fig. 7
Fig. 7

Aberration at the centered and marginal points on the detector for different t G-C = r T2 cos δ2 - 200: (a) 540 nm (left side), (b) 550 nm (center), and (c) 560 nm (right side).

Fig. 8
Fig. 8

Slit images of 100 µm × 100 µm by use of optimized parameters for the centered wavelength (550 nm) except L g-cd = L opt + 200 mm at (a) 540 nm (left end), (b) 550 nm (center), and (c) 560 nm (right).

Fig. 9
Fig. 9

Spot diagrams at various wavelengths (center, λ0) by use of the parameters optimized for λ0 = 550 nm: (a) λ0 = 404.5 nm, (b) λ0 = 650 nm, (c) λ0 = 730 nm, and (d) λ0 = 809 nm.

Fig. 10
Fig. 10

Spot diagrams at λ0 = 809 nm with different gratings by use of the optimum configuration λ0 = 550 nm: (a) with 1800 grooves/mm and (b) with 1200 grooves/mm.

Fig. 11
Fig. 11

Photo of the constructed spectrometer.

Fig. 12
Fig. 12

Spectral profile observed at 546.1 nm from a Hg emission line (a fiber probe of 100 µm was used to collect and was attached to the entrance slit) observed with the spectrometer.

Fig. 13
Fig. 13

Single-fiber image (a) with the spherical mirror for Mcd or (b) with the toroidal mirror.

Fig. 14
Fig. 14

Fiber bundle image observed at the center and marginal points of the detector in the designed spectrometer: (a) at 538.5 nm (left end), (b) at 546.0 nm (center), and (c) at 558.5 nm (right end). For images (a)–(c), the centered wavelength is adjusted so that the Hg line at 546.07 nm is located at the left end, center, and right end of the CCD detector. (d)–(f) Spectral profiles of the images (a)–(c).

Fig. 15
Fig. 15

Fiber bundle image observed at the center and marginal points of the detector in a conventional spectrometer (F/4.3): (a) at 520.0 nm (left end), (b) at 546.0 nm (center), and (c) at 580.0 nm (right end). Here the centered wavelength is adjusted so that the Hg line at 546.0 nm is located at the left end, center, and right end of the CCD detector [1024(x) × 256(y) pixels, with a size of 25 µm × 25 µm and with a grating of 1200 grooves/mm and f = 250 mm].

Fig. 16
Fig. 16

Fiber bundle images (ϕ = 100 µm, with a separation of 235 µm) observed at various wavelengths with the same parameters as in Figs. 7 and 12(a): (a) 404.5 nm, (b) 650 nm, 730 nm, and (d) 809 nm.

Fig. 17
Fig. 17

Fiber bundle image observed at various wavelengths with different gratings: (a) λ0 = 546 nm with 1800 grooves/mm, (b) 546 nm with 1200 grooves/mm, (c) 809 nm with 1800 grooves/mm, and (d) 809 nm with 1200 grooves/mm. Here the slit width is 100 µm.

Fig. 18
Fig. 18

Raman spectra observed from CuPc (1.5 nm)-Ag (5 nm)-BK-7 in ATR conditions (incident angle of approximately 60°) at 500–1000 cm-1 with the spectrometer. Laser power of 2–3 mW, p-polarized light, and a slit width of 100 µm were used for the Raman excitation.

Fig. 19
Fig. 19

Geometrical relation between the distance L g-cd and the incident angles to the condensing mirror for the centered light and marginal light.

Tables (1)

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Table 1 Optical Configuration of the Designed Spectrometer

Equations (9)

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sin δ2=r22/r12cos i cos δ2/cos θ cos δ13×sin δ1.
sin δ2=r22/r12cos i/cos θ3 sin δ1.
fTi=rTi/2cos δi,
fSi=rSi/2 cos δi.
λ=dsin i+sin θ=2d sin δ cos γ,δ=sin-1λ/2d cos γ.
Δλ/Δx=d cos θ/mf.
y-r2 sin δ2 cos δ2=tan-δ2+Δγ×x-r2 sin2 δ2.
y=tan Δγx.
x=r cos2 Δγ, y=r sin Δγ cos Δγ.

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