J. Chem. Chem. Eng.

7 (2013) 1117-1120

DAVID

PUBLISHING

LO-RAY-LIGH Diffraction Gratings in UV-VIS Spectroscopy

Uwe Oppermann1*, Marion Egelkraut-Holtus1 and Tatsuyoshi Fujiwara2
1. Shimadzu Europa GmbH, Duisburg D-47269, Germany 2. Shimadzu Device Corporation, Tokyo 101-8448, Japan Received: July 23, 2013 / Accepted: August 09, 2013 / Published: December 25, 2013. Abstract: It has been more than half a century since the release of the first Shimadzu UV-VIS (UV-visible) spectrophotometer QB-50 in 1952, and during this time more than 160,000 UV-VIS spectrometers have been produced and installed in a wide variety of different applications. A lot of technical innovations have been implemented to improve the performance and significantly reduce the stray light levels. The latest innovation during development of sophisticated spectrophotometers is based on a new holographic exposure method and optimized etching process which has made it possible to produce both high-efficient and exceptionally low stray light gratings. These LO-RAY-LIGH gratings have guaranteed values of stray light at the intermediate position between zero-order and first-order lights. The values are measured by Shimadzus laser stray-light-measuring system. The latest development in the series of UV-VIS spectrophotometers is the UV-2700 which is a true double beam double monochromator system in a compact design for high-precision spectral analysis of a wide range of samples including organic and inorganic compounds, biological samples, optical materials and photovoltaics. The high performance optical system is designed with LO-RAY-LIGH diffraction gratings, featuring highest efficiency and exceptionally low stray light. The spectrophotometer operates in the wavelength range from 185 nm to 900 nm and allows highly sophisticated applications such as direct measurement of high density samples up to 8 absorbance units without dilution. Key words: LO-RAY-LIGH, stray light, diffraction grating, spectrophotometer, single monochromator, holographic grating, high efficiency, double monochromator.

1. Introduction
Diffraction gratings have a history of more than 200 years that dates back to their discovery in 1785 by the American astronomer David Rittenhouse. He noticed that light seeping through a silk handkerchief formed the same colors as a rainbow and made a grating by wrapping hair around two parallel clock screws. At that time, however, his discovery was not recognized in the world. This phenomenon was rediscovered by Fraunhofer in 1819. Fraunhofers first grating consisted of fine wire wrapped around two parallel screws. He also used a diamond tool to make a reflective grating with 9,600 grooves across a width of 12 mm and derived the grating equations. In 1882,
* Corresponding author: Uwe Oppermann, Dipl. Min., research field: spectroscopy. E-mail: uo@shimadzu.eu.

Rowland constructed a ruling engine for production of diffraction gratings which could make 14,000 grooves per inch. Most of the gratings around this time were made by ruling grooves directly into metallic mirrors. Unfortunately the ruling engines of that time made large mechanical errors, until 1915, when Michelson came up with the idea of using light interference to control the positioning of grating grooves. Based on this technology, gratings became commercially available. In 1955, based on Harrisons developments [1], improvements in ruling engines made it possible to control the shape of the grooves, and concentrate most of the energy in lower orders of diffracted light. This type of grating is called a blazed grating and today is one of the most commonly used types. The last half-century saw many attempts to make

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LO-RAY-LIGH Diffraction Gratings in UV-VIS Spectroscopy

gratings by recording interference patterns of coherent light onto light sensitive material and finally the production of this type of grating became possible with the appearance of the argon ion laser and the high-resolution photoresist. Since Rudolph and Schmahls creation of the first grating of this type in 1967, this field has seen remarkable progress. Because of similarities with holography, this type of grating is called a holographic grating. Finally, in 1976, Aoyagi and Namba [2] succeeded in changing the profile of grooves from sinusoidal to sawtooth by etching diagonally with an ion beam. This made it possible to create blazed holographic gratings with any blaze angle, and such gratings are now used extensively in spectrometers.

2. Technology
A grating produced by a holographic exposure method that adopted the two beams interference of laser beam is called a HG (holographic grating). With holographic gratings, there is very little stray light due to periodic errors, and concave HG have the highly useful property of being able to correct aberrations within the grating itself. After many years of joint research together with the RIKEN (Rikagaku Kenkyjo) Institute of Physical and Chemical Research, Shimadzu Corporation succeeded in blazing a holographic grating, something that had previously been thought impossible, using ion-beam etching technology. Based on this, Shimadzu was the first to develop the technology for manufacturing BHG (blazed holographic gratings), which, compared to conventional mechanically ruled gratings, ensure less stray light without any reduction in diffraction efficiency (Fig. 1). This unique grating manufacturing technology was patented in Japan as Japanese patent No. 1046763 and was awarded the Okochi Memorial Prize. In order to facilitate more effective aberration correction for the wavelength region used in different types of gratings, Shimadzu developed an aspherical wave exposure

Fig. 1 Manufacturing process for blazed holographic gratings.

method that uses aspherical waves for holographic exposure method [3-7]. As a result, it is now possible to custom-design gratings of excellent performance to match the characteristics of different types of spectroscopic devices. 2.1 Stray Light Stray light in the optical system of a spectrophotometer is the measured quantity of light that reaches the detector that is of a wavelength other than the selected one. Therefore, the stray light which is generated during a transmission measurement is causing the results to be higher than expected. For example, when measuring the absorbance using light at 220 nm, accurate measurements are not possible if a lot of light at wavelengths other than 220 nm hit the

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sample. Let the authors consider the case of 0.01% stray light outside the specified wavelength. Due to the effects of the stray light, a sample with 1% transmittance (2 Abs) appears to have a transmittance of 1.01% (1.9957 Abs). Alternatively, a sample with 0.01% transmittance (4 Abs) appears to have a transmittance of 0.02% (3.6990 Abs). In the result, errors of 0.0043 Abs and 0.3010 Abs, respectively, occur. This case reveals that the effects of stray light increase as the sample absorbance increases [8]. The presence of stray light causes distortion in the calibration curve. Consequently, an instrument with low stray light is required for the quantitation of high-concentration unknown samples (with high absorbance) using a calibration curve created with standard samples. As a consequence, the stray light levels in the optics of a spectrophotometer must be as low as possible. The double beam spectrophotometer UV-2700 using a diffraction grating from the LO-RAY-LIGH design is equipped with a double monochromator optics, which achieves ultra-low stray light levels and makes the UV-2700 ideal for measuring low transmittance samples, such as polarization films used for LCD-panels. The UV-2700 is capable of 8-Abs measurements, and can make accurate transmittance measurements to 1 part in 100

million, accommodating measurements [9, 10].

variety

of

sample

2.2 New Holographic Exposure Method Shimadzu has optimized the quality of the edges for the angle of reflection in the sawtooth pattern. This LO-RAY-LIGH principle is a patented development that produces an outstanding grating quality. Until now, the generally accepted rule was: the more lines to a grating, the sharper the spectral image. With the LO-RAY-LIGH grating technology, this rule has changed. The production process of the grating results in a high grating image precision which also yields a spectral resolution sharpness rendering better characteristics when compared to a conventional grating. The objective in the development of these gratings was a significant reduction in stray light.

3. Results
Fig. 2 shows the stray light values for a LO-RAY-LIGH diffraction grating and a conventional diffraction grating. Two types of diffraction gratings were investigated: those with a groove density of 1,200 grooves/mm and a blaze wavelength at 250 nm and those with a groove density

Fig. 2 Representation of stray light and comparison between a conventional grating, a LO-RAY-LIGH grating and an aluminum reference mirror.

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LO-RAY-LIGH Diffraction Gratings in UV-VIS Spectroscopy

exceptional linear characteristics up to eight absorption units. Furthermore, the low stray light optics is ideal for applications with high absorptions, high linearity and low stray light such as polarizing films, transmission of functional films, thickness determination of thin films, protein and nucleic acid determination, environmental analysis, quantification of inorganic compounds in water and food analysis.

4. Conclusions
Fig. 3 Representation of the intensity of the first-order light as a function of the distance to the origin of the wavelengths in nm.

of 1,800 grooves/mm and a blaze wavelength at 250 nm (Fig. 2). It can be seen that the LO-RAY-LIGH diffraction gratings have far lower stray light values in comparison to the conventional type gratings. For the qualification of a grating, the intensity of the first-order light is plotted against delta (nm). From Fig. 3, it becomes evident that the LO-RAY-LIGH grating produces first-order light much more sharply and with less stray light over the entire range. In Fig. 3, a grating with 1,200 grooves/mm was compared with a blaze wavelength of 250 nm [11]. The quality of the optical components becomes noticeable during the measurement of high absorbance samples. The UV-2700 spectrophotometer is equipped with a double monochromator optical system containing two LO-RAY-LIGH gratings. The effect is significant. An example is the linearity measurement of a KMnO4 dilution series where the UV-2700 UV-VIS spectrophotometer features

Blazed holographic gratings provide the high diffraction efficiency for specific wavelengths in the ultraviolet and visible light. They can be used in a wide variety of spectrophotometers. Depending on the required application, the design of the optical system might be in single or double monochromator layout. In high performance optical systems, the double monochromator layout in combination with LO-RAY-LIGH diffraction gratings is the ideal solution.

Referencess
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] Harrison, G. R. J. Opt. Soc. Am. 1949, 39. Aoyagi, Y.; Namba, S. Opt. Acta 1976, 23, 701. Japanese Patent 1,946,518. U.S. Patent 5,052,766. U.K./French/German Patent 270,700. Chinese Patent 23,311. Singapore Patent No. 28,110. Talkletter, U. V. Shimadzu Corp 2011, 8, 2-4. Appl. News; Shimadzu Corp, 2012. Shimadzu News, 2013, 2, 16-17. Ihara, M. Shimadzu Rev. 2007, 64, 25-31.