The name colorimeter, and colourimeter, refers to an instrument used in colorimetry. This term can be applied to at least two related devices.
- In scientific fields the word generally refers to the device that measures the absorbance of particular wavelengths of light by a specific solution. This device is most commonly used to determine the concentration of a known solute in a given solution by the application of the Beer-Lambert law, which states that the concentration of a solute is proportional to the absorbance.
- In digital imaging, tristimulus colorimeters, also shortened to colorimeters, are used to profile and calibrate output devices.
(1) Wavelength selection, (2) Printer button, (3) Concentration factor adjustment, (4) UV mode selector (Deuterium lamp), (5) Readout, (6) Sample compartment, (7) Zero control (100% T), (8) Sensitivity switch.
The essential parts of a colorimeter are:
- a light source (often an ordinary low-voltage filament lamp)
- an adjustable aperture
- a set of colored filters
- a cuvette to hold the working solution
- a detector (usually a photoresistor) to measure the transmitted light
- a meter to display the output from the detector
In addition, there may be:
- a voltage regulator, to protect the instrument from fluctuations in mains voltage.
- a second light path, cuvette and detector. This enables comparison between the working solution and a “blank”, consisting of pure solvent, to improve accuracy.
Changeable optics filters are used in the colorimeter to select the wavelength of light which the solute absorbs the most, in order to maximize accuracy. The usual wavelength range is from 400 to 700 nanometres (nm). If it is necessary to operate in the ultraviolet range (below 400 nm) then some modifications to the colorimeter are needed. In modern colorimeters the filament lamp and filters may be replaced by several light-emitting diodes of different colors.
Main article: Cuvette
In a manual colorimeter the cuvettes are inserted and removed by hand. An automated colorimeter (as used in an AutoAnalyzer) is fitted with a flowcell through which solution flows continuously.
The output from a colorimeter may be displayed by an analogue or digital meter and may be shown as transmittance (a linear scale from 0-100%) or as absorbance (a logarithmic scale from zero to infinity). The useful range of the absorbance scale is from 0-2 but it is desirable to keep within the range 0-1 because, above 1, the results become unreliable due to scattering of light.
In addition, the output may be sent to a chart recorder, data logger, or computer.
The CIE 1931 XYZ color matching functions
A tristimulus colorimeter—colloquially shortened to colorimeter—takes a limited number of wideband spectral energy readings (~3-7) along the visible spectrum by using filtered photodetectors; e.g. silicon photodiodes.
Originally, three glass filters whose transmittance spectra mimicked the CIE color matching functions (shown on the right) were employed. A filter bank may be used to decompose the individual color matching functions if more accuracy is desired.
A camera or colorimeter is said to be colorimetric if it satisfies the Luther condition (also called the “Maxwell-Ives criterion”), reducing observer metamerism color errors, if the product of the spectral responsivity of the photoreceptor and the spectral transmittance of the filters is a linear combination of the CMFs.
A colorimeter or a digital camera with a color filter array can, under certain conditions, be used as an alternative to a spectrophotometer.
The illuminant and observer conditions should be specified when citing a measurement (e.g. D65/10°).
The quality of a colorimeter may be assessed using the means in CIE publication 179:2007.
In physics, spectrophotometry is the quantifiable study of electromagnetic spectra. It is more specific than the general term electromagnetic spectroscopy in that spectrophotometry deals with visible light, near-ultraviolet, and near-infrared. Also, the term does not cover time-resolved spectroscopic techniques.
Spectrophotometry involves the use of a spectrophotometer. A spectrophotometer is a photometer (a device for measuring light intensity) that can measure intensity as a function of the color, or more specifically, the wavelength of light. Important features of spectrophotometers are spectral bandwidth and linear range of absorption measurement.
Perhaps the most common application of spectrophotometers is the measurement of light absorption, but they can be designed to measure diffuse or specular reflectance. Strictly, even the emission half of a luminescence instrument is a kind of spectrophotometer.
The use of spectrophotometers is not limited to studies in physics. They are also commonly used in other scientific fields such as chemistry, biochemistry, and molecular biology. They are widely used in many industries including printing and forensic examination.
There are two major classes of spectrophotometers; single beam and double beam. A double beam spectrophotometer compares the light intensity between two light paths, one path containing a reference sample and the other the test sample. A single beam spectrophotometer measures the relative light intensity of the beam before and after a test sample is inserted. Although comparison measurements from double beam instruments are easier and more stable, single beam instruments can have a larger dynamic range and are optically simpler and more compact.
Historically, spectrophotometers use a monochromator containing a diffraction grating (In optics, a diffraction grating is an optical component with a regular pattern, which splits and diffracts light into several beams travelling in different directions. The directions of these beams depend on the spacing of the grating and the wavelength of the light so that the grating acts as a dispersive element. Because of this, gratings are commonly used in monochromators and spectrometers) to produce the analytical spectrum. There are also spectrophotometers that use arrays of photosensors. Especially for infrared spectrophotometers, there are spectrophotometers that use a Fourier transform technique to acquire the spectral information quicker in a technique called Fourier Transform InfraRed…
The spectrophotometer quantitatively compares the fraction of light that passes through a reference solution and a test solution. Light from the source lamp is passed through a monochromator, which difracts the light into a “rainbow” of wavelngths and outputs narrow bandwidths of this diffracted spectrum. Discrete frequencies are transmitted through the test sample. Then the intensity of the transmitted light is measured with a photodiode or other light sensor, and the transmittance value for this wavelength is then compared with the transmission through a reference sample.
In short, the sequence of events in a spectrophotometer is as follows:
- The light source shines into a monochromator.
- A particular output wavelength is selected and beamed at the sample.
- The sample absorbs light.
- The photodetector behind the sample responds to the light stimulus and outputs an analog electronic current which is converted to a usable format.
- The numbers are either plotted straight away, or are fed to a computer to be manipulated (e.g. curve smoothing, baseline correction and coversion to absorbency, a log function of light transmittance through the sample)
Many spectrophotometers must be calibrated by a procedure known as “zeroing.” The absorbency of a reference substance is set as a baseline value, so the absorbencies of all other substances are recorded relative to the initial “zeroed” substance. The spectrophotometer then displays % absorbency (the amount of light absorbed relative to the initial substance).
UV and IR spectrophotometers
The most common spectrophotometers are used in the UV and visible regions of the spectrum, and some of these instruments also operate into the near-infrared region as well.
Visible region 400-700 nm spectrophotometry is used extensively in colorimetry science. Ink manufacturers, printing companies, textiles vendors, and many more, need the data provided through colorimetry. They take readings in the region of every 10- 20 nanometers along the visible region, and produce a spectral reflectance curve or a data stream for alternative presentations. These curves can be used to test a new batch of colorant to check if it makes a match to specifications e.g., iso printing standards.
Traditional visual region spectrophotometers cannot detect if a colorant or the base material has fluorescence. This can make it difficult to manage color issues if for example one or more of the printing inks is fluorescent. Where a colorant contains fluorescence, a bi-spectral fluorescent spectrophotometer is used. There are two major setups for visual spectrum spectrophotometers, d/8 (spherical) and 0/45. The names are due to the geometry of the light source, observer and interior of the measurement chamber. Scientists use this machine to measure the amount of compounds in a sample. If the compound is more concentrated more light will be absorbed by the sample; within small ranges, the Beer-Lambert law holds and the absorbance between samples vary with concentration linearly. In the case of printing measurements to alternative settings are commonly used- without/with uv filter to control better the effect of uv brighteners within the paper stock.
Samples are usually prepared in cuvettes; depending on the region of interest, they may be constructed of glass, plastic, or quartz.
Spectrophotometers designed for the main infrared region are quite different because of the technical requirements of measurement in that region. One major factor is the type of photosensors that are available for different spectral regions, but infrared measurement is also challenging because virtually everything emits IR light as thermal radiation, especially at wavelengths beyond about 5 ?m.
Another complication is that quite a few materials such as glass and plastic absorb infrared light, making it incompatible as an optical medium. Ideal optical materials are salts, which do not absorb strongly. Samples for IR spectrophotometry may be smeared between two discs of potassium bromide or ground with potassium bromide and pressed into a pellet. Where aqueous solutions are to be measured, insoluble silver chloride is used to construct the cell.
Spectroradiometers, which operate almost like the visible region spectrophotometers, are designed to measure the spectral density of illuminants in order to evaluate and categorize lighting for sales by the manufacturer, or for the customers to confirm the lamp they decided to purchase is within their specifications. Components:
- The light source shines onto or through the sample.
- The sample transmits or reflects light.
- The detector detects how much light was reflected from or transmitted through the sample.
- The detector then converts how much light the sample transmitted or reflected into a number.
A monochromator is an optical device that transmits a mechanically selectable narrow band of wavelengths of light or other radiation chosen from a wider range of wavelengths available at the input. The name is from the Greek roots mono-, single, and chroma, colour, and the Latin suffix -ator, denoting an agent.
A device that can produce monochromatic light has many uses in science and in optics because many optical characteristics of a material are dependent on color. Although there are a number of useful ways to produce pure colors, there are not so many other ways to easily select any pure color in a wide range. See below for a discussion of some of the uses of monochromators.
In hard X-ray and neutron optics, crystal monochromators are used to define wave conditions on the instruments.
A monochromator can use either the phenomenon of optical dispersion in a prism, or that of diffraction using a diffraction grating, to spatially separate the colors of light. It usually has a mechanism for directing the selected color to an exit slit. Usually the grating or the prism are used in a reflective mode. A reflective prism is made by making a right triangle prism (typically, half of an equilateral prism) with one side mirrored. The light enters through the hypotenuse face and is reflected back through it, being refracted twice at the same surface. The total refraction, and the total dispersion, is the same as would occur if an equilateral prism were used.
The dispersion or diffraction is only controllable if the light is collimated, that is if all the rays of light are parallel, or practically so. A source, like the sun, which is very far away, provides collimated light. Newton used sunlight in his famous experiments. In a practical monochromator however, the light source is close by, and an optical system in the monochromator converts the diverging light of the source to collimated light. Although some monochromator designs do use focusing gratings that do not need separate collimators, most use collimating mirrors. Reflective optics are preferred because they do not introduce dispersive effects of their own.
A Fastie-Ebert monochromator. This is similar to the Czerny-Turner but uses a common collimator/refocusing mirror.
In the common Czerny-Turner design, the broad band illumination source (A) is aimed at an entrance slit (B). The amount of light energy available for use depends on the intensity of the source in the space defined by the slit (width * height) and the acceptance angle of the optical system. The slit is placed at the effective focus of a curved mirror (the collimator, C) so that the light from the slit reflected from the mirror is collimated (focused at infinity). The collimated light is refracted by the prism or diffracted from the grating (D) and then is collected by another mirror (E) which refocuses the light, now dispersed, on the exit slit (F). At the exit slit, the colors of the light are spread out (in the visible this shows the colors of the rainbow). Because each color arrives at a separate point in the exit slit plane, there are a series of images of the entrance slit focused on the plane. Because the entrance slit is finite in width, parts of nearby images overlap. The light leaving the exit slit (G) contains the entire image of the entrance slit of the selected color plus parts of the entrance slit images of nearby colors. A rotation of the dispersing element causes the band of colors to move relative to the exit slit, so that the desired entrance slit image is centered on the exit slit. The range of colors leaving the exit slit is a function of the width of the slits. The entrance and exit slit widths are adjusted together.
The ideal transfer function of such a monochromator is a triangular shape. The peak of the triangle is at the nominal wavelength selected. The intensity of the nearby colors then decreases linearly on either side of this peak until some cutoff valuedi is reached, where the intensity stops decreasing. This is called the stray light level. The cutoff level is typically about one thousandth of the peak value, or 0.1%.
A typical spectral bandwidth might be one nanometer, which is defined as the width of the triangle at the points where the light has reached half the maximum value. Thus spectral bandwidth is defined as Full Width at Half Maximum abbreviated FWHM.
The dispersion of a monochromator is characterized as the width of the band of colors per unit of slit width, 1 nm of spectrum per mm of slit width for instance. This factor is constant for a grating, but varies with wavelength for a prism. If a scanning prism monochromator is used in a constant bandwidth mode, the slit width must change as the wavelength changes.
A monochromator’s adjustment range might cover the visible spectrum and some part of both or either of the nearby ultraviolet (UV) and infrared (IR) spectra, although monochromators are built for a great variety of optical ranges, and to a great many designs.
It is common for two monochromators to be connected in series, with their mechanical systems operating in tandem so that they both select the same color. This arrangement is not intended to improve the narrowness of the spectrum, but rather to lower the cutoff level. A double monochromator may have a cutoff about one millionth of the peak value, the product of the two cutoffs of the individual sections. The intensity of the light of other colors in the exit beam is referred to as the stray light level and is the most critical specification of a monochromator for many uses. Achieving low stray light is a large part of the art of making a practical monochromator.
Diffraction gratings & Blazed gratings
When a diffraction grating is used, care must be taken in the design of broad band monochromators because the diffraction pattern has overlapping orders. Sometimes extra, broadband filters are inserted in the optical path to limit the width of the diffraction orders so they do not overlap. Sometimes this is done by using a prism in one of the monochromators of a dual monochromator design.
The original high resolution diffraction gratings were ruled. The construction of high quality ruling engines was a large undertaking, and good gratings were very expensive. The slope of the triangular groove in a ruled grating is typically adjusted to enhance the brightness of a particular diffraction order. This is called blazing a grating. Ruled gratings have imperfections that produce faint “ghost” diffraction orders that may raise the stray light level of a monochromator. A later photolithographic technique allows gratings to be created from a holographic interference pattern. Holographic gratings have sinusoidal grooves and so are not as bright, but have lower scattered light levels than blazed gratings. Almost all the gratings actually used in monochromators are carefully made replicas of ruled or holographic master gratings.
Prisms have higher dispersion in the UV region. Prism monochromators are favored in some instruments that are principally designed to work in the far UV region. Most monochromators use gratings though. Some monochromators have several gratings that can be selected for use in different spectral regions. A double monochromator made by placing a prism and a grating monochromator in series typically does not need additional bandpass filters to isolate a single grating order.
The narrowness of the band of colors that a monochromator can generate is related to the focal length of the monochromator collimators. Using a longer focal length optical system also unfortunately decreases the amount of light that can be accepted from the source. Very high resolution monochromators might have a focal length of 2 meters. Building such monochromators requires exceptional attention to mechanical and thermal stability. For many applications a monochromator of about 0.4 meter focal length is considered to have excellent resolution. Many monochromators have a focal length less than 0.1 meter.
The most common optical system uses spherical collimators and thus contains optical aberrations that curve the field where the slit images come to focus, so that slits are sometimes curved instead of simply straight, to approximate the curvature of the image. This allows taller slits to be used, gathering more light, while still achieving high spectral resolution. Some designs take another approach and use toroidal collimating mirrors to correct the curvature instead, allowing higher straight slits without sacrificing resolution.
Wavelength vs Energy
Monochromators are often calibrated in units of wavelength. Uniform rotation of a grating produces a linear change in wavelength, so such an instrument is easy to build. Many of the underlying physical phenomena being studied are linear in energy though, and since wavelength and energy have a reciprocal relationship, spectral patterns that are simple and predictable when plotted as a function of energy are distorted when plotted as a function of wavelength. Some monochromators are calibrated in units of reciprocal centimeters or some other energy units, but the scale may not be linear.
A spectrophotometer built with a high quality double monochromator can produce light of sufficient purity and intensity that the instrument can measure a narrow band of optical attenuation of about one million fold (6 AU).
Monochromators are used in many optical measuring instruments and in other applications where tunable monochromatic light is wanted. Sometimes the monochromatic light is directed at a sample and the reflected or transmitted light is measured. Sometimes white light is directed at a sample and the monochromator is used to analyze the reflected or transmitted light. Two monochromators are used in many fluorometers; one monochromator is used to select the excitation wavelength and a second monochromator is used to analyze the emitted light.
An automatic scanning spectrometer includes a mechanism to change the wavelength selected by the monochromator and to record the resulting changes in the measured quantity as a function of the wavelength.
If an imaging device replaces the exit slit, the result is the basic configuration of a spectrograph. This configuration allows the simultaneous analysis of the intensities of a wide band of colors. Photographic film or an array of photodetectors can be used, for instance to collect the light. Such an instrument can record a spectral function without mechanical scanning, although there may be tradeoffs in terms of resolution or sensitivity for instance.
An absorption spectrophotometer measures the absorption of light by a sample as a function of wavelength. Sometimes the result is expressed as percent transmission and sometimes it is expressed as the inverse logarithm of the transmission. The Beer-Lambert law relates the absorption of light to the concentration of the light-absorbing material, the optical path length, and an intrinsic property of the material called molar absorptivity. According to this relation the decrease in intensity is exponential in concentration and path length. The decrease is linear in these quantities when the inverse logarithm of transmission is used. The old nomenclature for this value was Optical Density (OD), current nomenclature is Absorbance Units (AU). One AU is a tenfold reduction in light intensity. Six AU is a millionfold reduction.
Absorption spectrophotometers often contain a monochromator to supply light to the sample. Some absorption spectrophotometers have automatic spectral analysis capabilities.
Absorption spectrophotometers have many everyday uses in chemistry, biochemistry, and biology. For example, they are used to measure the concentration or change in concentration of many substances that absorb light. Critical characteristics of many biological materials, many enzymes for instance, are measured by starting a chemical reaction that produces a color change that depends on the presence or activity of the material being studied. Optical thermometers have been created by calibrating the change in absorbance of a material against temperature. There are many other examples.
Spectrophotometers are used to measure the specular reflectance of mirrors and the diffuse reflectance of colored objects. They are used to characterize the performance of sunglasses, laser protective glasses, and other optical filters. There are many other examples.
In the UV, visible and near IR, absorbance and reflectance spectrophotometers usually illuminate the sample with monochromatic light. In the corresponding IR instruments, the monochromator is usually used to analyze the light coming from the sample.
Monochromators are also used in optical instruments that measure other phenomena besides simple absorption or reflection, wherever the color of the light is a significant variable. Circular dichroism spectrometers contain a monochromator, for example.
Lasers produce light which is much more monochromatic than the optical monochromators discussed here, but only some lasers are easily tunable, and these lasers are not as simple to use.
Monochromatic light allows for the measurement of the Quantum Efficiency (QE) of an imaging device (e.g. CCD or CMOS imager). Light from the exit slit is passed either through diffusers or an integrating sphere on to the imaging device while a calibrated detector simultaneously measures the light. Coordination of the imager, calibrated detector, and monochromator allows one to calculate the carriers (electrons or holes) generated for a photon of a given wavelength, QE.
A polychromator, more generally known as a spectrograph, is an optical device that is used to disperse light into different directions to isolate parts of the spectrum of the light. A prism or diffraction grating can be used to disperse the light. Unlike a monochromator, it outputs multiple beams over a range of wavelengths simultaneously. Polychromators are often used in spectroscopy.