Ultraviolet and Blue Fluorescence Emitted by Integrating Spheres

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Figure 1: Typical yields at each wavelength are around four orders of magnitude lower than the excitation wavelength. [4]

The spectral fluorescence yield relates the intensity of the fluorescence emitted within the integrating sphere with the intensity of the excitation wavelength. The yield is calculated by dividing the wavelength-dependent, total fluorescence excited over the entire interior surface of the sphere by the intensity of the light excitation.

Data were kindly provided by Dr. Ping-Shine Shaw, Physics Laboratory, National Institute of Standards and Technology, Gaithersburg, MD 20899, USA.

A material of choice for coating the light-diffusing cavities of integrating spheres is polytetrafluoroethylene (PTFE). This material, which is white in appearance, is favored for reasons including its high, flat reflectance over a wide range of wavelengths and chemical inertness.

However, it should be noted that integrating spheres coated with both PTFE and barium sulfate, which is an alternative coating with lower reflectance, emit low levels of ultraviolet (UV) and blue fluorescence when irradiated by UV light. [1-3]

Hydrocarbons in the PTFE Fluoresce
It is not the PTFE that fluoresces. The sources of the UV and blue fluorescence are hydrocarbons in the PTFE. Low levels of hydrocarbon impurities are present in the raw coating material, and pollution sources deposit additional hydrocarbon contaminants in the PTFE material of the integrating sphere during its use and storage. [1]

Fluorescence Wavelength Bands and Strength
Researchers at the National Institute of Standards and Technology (NIST) have investigated the fluorescence excited by illuminating PTFE-coated integrating spheres. The total fluorescence output by the integrating sphere was measured with respect to fluorescence wavelength and excitation wavelength. The maximum fluorescence was approximately four orders of magnitude lower than the intensity of the exciting radiation.

The UV and blue fluorescence from PTFE is primarily excited by incident wavelengths in a 200 nm to 300 nm absorption band. The fluorescence is emitted in the 250 nm to 400 nm wavelength range, as shown by Figure 1. These data indicate that increasing the excitation wavelength decreases the fluorescence emitted at lower wavelengths and changes the shape of the fluorescence spectrum.

As the levels of hydrocarbon contaminants in the PFTE increase, fluorescence increases. A related effect is a decrease of the light output by the integrating sphere over the absorption band wavelengths, due to more light from this spectral region being absorbed. [1, 3]

Impact on Applications
The UV and blue fluorescence from the PTFE has negligible effect on many applications, since the intensity of the fluorescence is low and primarily excited by incident wavelengths <300 nm. Applications sensitive to this fluorescence include long-term measurements of UV radiation throughput, UV source calibration, establishing UV reflectance standards, and performing some UV remote sensing tasks. [1]

Minimizing Fluorescence Effects
Minimizing and stabilizing the fluorescence levels requires isolating the integrating sphere from all sources of hydrocarbons, including gasoline- and diesel-burning engine exhaust and organic solvents, such as naphthalene and toluene. It should be noted that, while hydrocarbon contamination can be minimized and reduced, it cannot be eliminated. [1]

Since the history of each integrating sphere's exposure to hydrocarbon contaminants is unique, it is not possible to predict the response of a particular sphere to incident radiation. When an application is negatively impacted by the fluorescence, calibration of the integrating sphere is recommended. A calibration procedure described in [4] requires a light source with a well-known spectrum that extends across the wavelength region of interest, such as a deuterium lamp or synchrotron radiation, a monochromator, a detector, and the integrating sphere.

References
[1] Ping-Shine Shaw, Zhigang Li, Uwe Arp, and Keith R. Lykke, "Ultraviolet characterization of integrating spheres," Appl.Opt. 46, 5119-5128 (2007).
[2] Jan Valenta, "Photoluminescence of the integrating sphere walls, its influence on the absolute quantum yield measurements and correction methods," AIP Advances 8, 102123 (2018).
[3] Robert D. Saunders and William R. Ott, "Spectral irradiance measurements: effect of UV-produced fluorescence in integrating spheres," Appl. Opt. 15, 827-828 (1976).
[4] Ping-Shine Shaw, Uwe Arp, and Keith R. Lykke, "Measurement of the ultraviolet-induced fluorescence yield from integrating spheres," Metrologia 46, S191 - S196 (2009).