Handheld Raman spectrometers are truly like no other analytical chemical instruments. All spectrometers (e.g., IR/NIR, UV-Vis, GC/MS, and Raman) rely on interactions between matter and energy and include detectors that collect information about resulting atomic and molecular changes. This information is used to qualify and/or quantify various chemical species. Typically, a spectrometer is a benchtop instrument attached to a computer or other visual display that is used by an analyst in a laboratory.
Raman is a unique investigative analytical technique in many ways. It is said, «If you can see it, Raman can ID it.»
Indeed, Raman’s strengths are its simple sampling methods combined with its specificity. Direct analysis is possible for many pure substances without sample preparation. Sampling is performed via direct contact with a substance, remotely, or through a barrier. Even solutes in water may be directly identified. This technique is highly specific; each material investigated with Raman produces a unique «fingerprint» spectrum. Raman spectroscopy is successful at positively identifying each distinct substance, while accurately rejecting even very similar compounds.
The Raman spectrum
Raman spectra contain peaks across a range that correspond to specific molecular connectivity and can be used to determine the chemical composition of a sample. The spectral range is dependent on spectrometer design, and embodies a balance of resolution and sensitivity.
The «fingerprint region» (400–1800 cm-1) is used to identify unknowns and verify known materials. The region below 400 cm-1 is helpful in the analysis of minerals, gemstones, metals, and semiconductors. For most organic materials (e.g., oils, polymers, plastics, proteins, sugars/starches, alcohols, solvents, etc.), very little information above 2255 cm-1 is useful in Raman applications, as carbon-hydrogen chains contribute little to molecular qualification.
MIRA’s measuring range
of 400–2300 cm-1 is perfect for most Raman applications, including:
- Pharma & other regulated industries
- Personal care & cosmetics
- Defense & security
- Process analytics
- Materials ID
- Education & research
Good things come in small packages
Technology, analysis, ease of use, accuracy—handheld Raman has all of this in a small format that escapes the confines of the lab. It also invites many new types of users who employ Raman for vastly new and exciting applications. In the rest of this blog post, I share details about the development of components that led to miniaturization of Raman. This is followed by the origin story of Metrohm Raman, manufacturer of MIRA (Metrohm Instant Raman Analyzers).
Four significant innovations came together to create MIRA: diode lasers, specialized filters and gratings, on-axis optics, and the CCD (Charge Coupled Device) in a unique design called the «astigmatic spectrograph». These basic components of a Raman spectrograph can be seen in the graphical representation above. Note that this is not an accurate depiction of the unique geometries found within MIRA’s case!
Raman spectroscopy is a technique which relies on the excitation of molecules with light (energy). C.V. Raman’s discovery of Raman scattering in 1928 was enabled by focused sunlight, which was then quickly replaced with a mercury lamp for excitation and photographic plates for detection. This resulted in a simple, popular, and effective method to determine the structure of simple molecules.
The first commercial Raman spectrometer was available in the 1950’s. As lasers became more available in the 1960’s, followed by improved filter technology in the 1970’s, Raman grew in popularity as a technique for a wide range of chemical analysis. Integrated systems were first seen in the 1990’s, and the miniaturization of instruments began in the early 2000’s.
Miniaturization of Raman spectrometers
Diode lasers were the first step toward handheld Raman. For those of you at a certain age, you may remember that these are the kind of small, cool, low energy lasers used in CD players, stabilized at the source with a unique kind of diffraction grating.
Powerful, efficient optical filters also contribute to miniaturization by controlling laser light scattering within the spectrograph. The development of sensitive, small Charge Coupled Devices (CCDs), which are commonly used in mobile phone cameras, permitted the detection of Raman scattering and efficient transmission of the resulting signals to a computer for processing.
The astigmatic spectrograph simplified both geometry and alignment for the many components within a Raman spectrometer; this design was the final advancement in the development of handheld Raman.
From Wyoming to Switzerland
By the 1990’s, new technologies developed for diverse industries were being incorporated into Raman spectroscopy. In Laramie, WY (USA) at the time, Dr. Keith Carron was a professor of Analytical Chemistry with a focus on Surface Enhanced Raman Scattering (SERS). Dr. Carron already had robust SERS tests, but he envisioned a low-cost Raman system that would introduce his tests to industrial, medical, or defense and security markets. His next steps would revolutionize Raman spectroscopy.
Using commercial off-the-shelf parts, Dr. Carron and his team developed an economical benchtop instrument that eliminated the high cost of Raman analysis, helping to enable its use in university curricula. In the early 2000’s, a research and education boom began as Raman grew from an esoteric technique used in high-end applications to becoming widely available for all kinds of tasks. Dr. Carron is responsible for ushering Raman into the current era. A collaboration led to a portable Raman system and, ultimately, to a new astigmatic spectrograph design in a very small instrument.
The U.S. tragedies on September 11, 2001 created an immediate push for technology to detect terrorist activity. Around this time, anthrax scares further enforced the need for «white powder» analyzers. Fieldable chemical analysis became the goal to achieve.
Dr. Carron was inspired to invent a truly handheld, battery powered Raman device for the identification of explosives and other illicit materials. A number of iterations led to CBex, a palm-sized Raman system (even smaller than MIRA!) designed by Snowy Range Industries, in February 2012. CBex caught the attention of Metrohm AG, and an offer of cooperation was sent to Dr. Carron in August 2013.
Along comes MIRA
MIRA was born in 2015. Not only is it a novel analytical instrument, but it is also unique amongst handheld Raman spectrometers. MIRA has the smallest form factor of all commercially available Raman instruments.
What truly sets MIRA apart from the competition is its built-in Smart Acquire routines, which provide anyone, anywhere, access to highly accurate analytical results. It is rugged, meeting MIL-STD 810G and IP67 specifications—you can drop MIRA or submerge it in a liquid to get an ID.
Once Raman escaped the confines of the laboratory, it suddenly had the potential for new uses by non-technical operators, who could perform highly analytical tests safely, quickly, and accurately.
In fact, miniaturization of Raman has revolutionized safety in a number of ways:
- Direct analysis eliminates dangers from exposure to laboratory solvents and other chemicals.
- Through-packaging analysis prevents user contact with potentially hazardous materials.
- Simplified on-site materials ID verifies the quality of ingredients in foods, medicines, supplements, cosmetics, and skin care products.
- ID of illicit materials such as narcotics, explosives, and chemical warfare agents supports quick action by military and civilian agencies.
I hope that you have enjoyed learning about the evolution of Raman technology from benchtop systems to the handheld instruments we have today. We continue to publish more articles about MIRA that describe, in detail, several interesting applications of handheld Raman spectroscopy. Find a selection of these articles below: