Dynamic Secondary Ion Mass Spectrometry Research Articles

Development of organic SIMS system with Ar‐GCIB and IMS‐4f

We have developed Ar‐gas cluster ion beam (GCIB) dynamic secondary ion mass spectrometry system by introducing Ar‐GCIB column to IMS‐4f. Mass spectrums of arginine and polystyrene (PS) are obtained with typical fragment ions. Depth profiles of PS are obtained within 10 nm depth resolutions. Secondary ion images of fine‐patterned PS are observed within 10 µm image resolutions. Copyright © 2014 John Wiley & Sons, Ltd.

Enhancing fullerene-based solar cell lifetimes by addition of a fullerene dumbbell.

Cost-effective, solution-processable organic photovoltaics (OPV) present an interesting alternative to inorganic silicon-based solar cells. However, one of the major remaining challenges of OPV devices is their lack of long-term operational stability, especially at elevated temperatures. The synthesis of a fullerene dumbbell and its use as an additive in the active layer of a PCDTBT:PCBM-based OPV device is reported. The addition of only 20 % of this novel fullerene not only leads to improved device efficiencies, but more importantly also to a dramatic increase in morphological stability under simulated operating conditions. Dynamic secondary ion mass spectrometry (DSIMS) and TEM are used, amongst other techniques, to elucidate the origins of the improved morphological stability.

Effects of the temperature and beam parameters on depth profiles in X-ray photoelectron spectrometry and secondary ion mass spectrometry under C60+–Ar+ cosputtering

Polymethylmethacrylate (PMMA) is widely used in various fields, including the semiconductor, biomaterial and microelectronic fields. Obtaining the correct depth profiles of PMMA is essential, especially when it is used as a thin-film. There have been many studies that have used earlier generation of cluster ion (SF5+) as the sputtering source to profile PMMA films, but few reports have discussed the use of the more recently developed C60+ in the PMMA sputtering process. In this study, X-ray photoelectron spectroscopy (XPS) and dynamic secondary ion mass spectroscopy (D-SIMS) were used concurrently to monitor the depth profiles of PMMA under C60+ bombardment. Additionally, the cosputtering technique (C60+ sputtering with auxiliary, low-kinetic-energy Ar+) was introduced to improve the analytical results. The proper cosputtering conditions could eliminate the signal enhancement near the interface that occurred with C60+ sputtering and enhance the sputtering yield of the characteristic signals. Atomic force microscopy (AFM) was also used to measure the ion-induced topography. Furthermore, the effect of the specimen temperature on the PMMA depth profile was also examined. At higher temperatures (+120°C), the depolymerization reaction that corresponded to main-chain scission dominated the sputtering process. At lower temperatures (−120°C), the cross-linking mechanism was retarded significantly due to the immobilization of free radicals. Both the higher and lower sample temperatures were found to further improve the resulting depth profiles.

Temperature-dependent wear mechanisms for magnetron-sputtered AlTiTaN hard coatings.

AlTiTaN coatings have been demonstrated to have high thermal stability at temperatures up to 900 °C. It has been speculated that the high oxidation resistance promotes an improved wear resistance, specifically for dry machining applications. This work reports on the influence of temperature up to 900 °C on the wear mechanisms of AlTiTaN hard coatings. DC magnetron-sputtered coatings were obtained from an Al(46)Ti(42)Ta(12) target, keeping the substrate bias at -100 V and the substrate temperature at 265 °C. The coatings exhibited a single-phase face-centered cubic AlTiTaN structure. The dry sliding tests revealed predominant abrasion and tribo-oxidation as wear mechanisms, depending on the wear debris formed. At room temperature, abrasion leading to surface polishing was observed. At 700 and 800 °C, slow tribo-oxidation and an amorphous oxide formed reduced the wear rate of the coating compared to room temperature. Further, an increase in temperature to 900 °C increased the wear rate significantly due to fast tribo-oxidation accompanied by grooving. The friction coefficient was found to decrease with temperature increasing from 700 to 900 °C due to the formation of oxide scales, which reduce adhesion of asperity contacts. A relationship between the oxidation and wear mechanisms was established using X-ray diffraction, Raman spectroscopy, scanning electron microscopy, surface profilometry, confocal microscopy, and dynamic secondary ion mass spectrometry.

Quantification and micron-scale imaging of spatial distribution of trace beryllium in shrapnel fragments and metallurgic samples with correlative fluorescence detection method and secondary ion mass spectrometry (SIMS).

Recently, a report raised the possibility of shrapnel-induced chronic beryllium disease from long-term exposure to the surface of retained aluminum shrapnel fragments in the body. Since the shrapnel fragments contained trace beryllium, methodological developments were needed for beryllium quantification and to study its spatial distribution in relation to other matrix elements, such as aluminum and iron, in metallurgic samples. In this work, we developed methodology for quantification of trace beryllium in samples of shrapnel fragments and other metallurgic sample-types with main matrix of aluminum (aluminum cans from soda, beer, carbonated water and aluminum foil). Sample preparation procedures were developed for dissolving beryllium for its quantification with the fluorescence detection method for homogenized measurements. The spatial distribution of trace beryllium on the sample surface and in 3D was imaged with a dynamic secondary ion mass spectrometry instrument, CAMECA IMS 3f secondary ion mass spectrometry ion microscope. The beryllium content of shrapnel (∼100 ppb) was the same as the trace quantities of beryllium found in aluminum cans. The beryllium content of aluminum foil (∼25 ppb) was significantly lower than cans. SIMS imaging analysis revealed beryllium to be distributed in the form of low micron-sized particles and clusters distributed randomly in X-Y- and Z dimensions, and often in association with iron, in the main aluminum matrix of cans. These observations indicate a plausible formation of Be-Fe or Al-Be alloy in the matrix of cans. Further observations were made on fluids (carbonated water) for understanding if trace beryllium in cans leached out and contaminated the food product. A direct comparison of carbonated water in aluminum cans and plastic bottles revealed that beryllium was below the detection limits of the fluorescence detection method (∼0.01 ppb). These observations indicate that beryllium present in aluminum matrix was either present in an immobile form or its mobilization into the food product was prevented by a polymer coating on the inside of cans, a practice used in food industry to prevent contamination of food products. The lack of such coating in retained shrapnel fragments renders their surface a possible source of contamination for long-term exposure of tissues and fluids and induction of disease, as characterized in a recent study. Methodological developments reported here can be extended to studies of beryllium in electronics devices and components.

Proximity Gettering of Copper via Oxygen Precipitates for Silicon-on-Insulator Wafer

Silicon-on-insulator (SOI) technology has attributed attention because it enables device to operate in high speed with reducing parasitic capacitance and body effect. However, in the conventional SOI wafer without any gettering site, a very small amount of metallic contaminants degrades the transistor. During fabrication of copper through-silicon-via (TSV) for 3D device structure, copper contaminants after copper damascene chemical-mechanical-polishing (CMP) are accumulated at top silicon layer, BOX layer and silicon substrate resulting in gate oxide leakage, junction leakage current, and threshold voltage shift, etc. Particularly, since the copper solubility in oxide layer is higher than that in silicon, the implementation of gettering sites for copper contaminants in SOI wafers is fundamentally difficult. Thus, a design of gettering for copper contaminants in SOI wafers has been a key engineering to improve device characteristics. In this study, we investigated the effect of oxygen precipitates, produced by rapid-thermal annealing (RTA), on gettering efficiency of copper for SOI wafers after a dynamic-random-access-memory (DRAM) heat-treatment. To design a desirable distribution of oxygen precipitates for the gettering sites, the wafers were subjected to a RTA at 1150, 1175 and 1200 ºC for 10 s in an NH3 and Ar gas mixture. In addition, the substrate wafers were annealed at 800 ºC for 4 h in a nitrogen ambient to grow the oxygen precipitates and then followed at 1000 ºC for 16 h. Then, the bonded SOI wafers with proximity gettering sites and conventional SOI wafer were intentionally contaminated with copper of 1 × 1012 atoms/cm2 on the wafer surface, and then all SOI wafers were subjected to a typical DRAM heat-treatment. We correlated concentration of the oxygen precipitate with gettering efficiency of copper contaminants. Figure. 1 shows the distribution of bulk micro defects (BMDs) in the substrate wafer with a different heat-treatment condition. It shows that the substrate wafer subjected to a RTA and two-step heat-treatment has the highest density of BMDs. A SOI wafer was conventionally fabricated and subjected to a DRAM heat-treatment after copper contamination intentionally. In this wafer, concentration of copper contaminants was measured via dynamic secondary ion mass spectroscopy (D-SIMS). As shown in Fig. 2, concentration of copper on top silicon, BOX layer and bulk silicon is high because there is no gettering site. In Fig. 3, a substrate wafer was subjected to a RTA at 1175 ºC for 10 s and then followed two-step heat-treatment. The concentration of copper contaminants was relatively lower than that of Fig 2. This means that coppers were well gathered at oxygen precipitates located at underneath buried oxide after DRAM heat-treatment, verifying an excellent gettering efficiency for copper contaminants. In our presentation, we will discuss the detailed gettering mechanism for copper contaminants in SOI wafers and report proximity gettering of copper via oxygen precipitates for SOI wafer.* This work was financially supported by the Brain Korea 21 Plus Program in 2013 and SiWEDS (Silicon Wafer Engineering and Defect Science).Reference[1] S.M. Myers et al., J. Appl. Phys. 88 (2000) 3795[2] Lixia Lin et al., Solid-State and Integrated Circuit Technology (2010) 1563

High-performance of PEDOT/PSS free organic solar cells on an air-plasma-treated ITO substrate.

In this work, we demonstrate the high-performance of a PEDOT:PSS free organic photovoltaic cell (OPVC) using an air-plasma modified ITO surface, followed by controlled solvent evaporation and annealing of the P3HT:PCBM photoactive layer. Ultraviolet photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS), and conductive atomic force microscopy (c-AFM) results show that the work function of ITO was increased to as high as that of PEDOT:PSS (5.2 eV) after air-plasma treatment, along with significantly enhanced electrical homogeneity. From the dynamic secondary ion mass spectroscopy (DSIMS) results, we confirm that the thermodynamic stability of the slow-dried active layer is attributed to the uniform vertical compositional distribution on the air plasma treated ITO surface, even after thermal annealing at 150 °C for 10 min. The resulting device has an open-circuit voltage of 0.65 V, a fill factor of 63%, and a power conversion efficiency of 3.38%, providing a high performance PEDOT:PSS free OPVC device.

Structural and optoelectronic properties of hybrid bulk-heterojunction materials based on conjugated small molecules and mesostructured TiO2

Improved hybrid bulk-heterojunction materials was fabricated by spin-casting a benchmark conjugated small molecule, namely, 3,6-bis(5-(benzofuran-2-yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DPP(TBFu)2), into mesostructured TiO2. Due to both a reduced molecular size and less hydrophobic nature of the conjugated molecules (relative to conjugated polymers), homogeneous and improved infiltration into the mesoporous TiO2 are achieved without the need for pre-treatment of the TiO2. Remarkably, this small molecule can realize loadings of up to 25% of the total pore volume—2.5× the typical loadings achieved for conjugated polymers. The small molecule loading was determined using dynamic secondary ion mass spectroscopy and absorption spectroscopy. Further characterization such as charge transfer and nanoscale conducting atomic force microscopy helps to demonstrate the promise and viability of small molecule donors for hybrid optoelectronic devices.

Influence of Temperature on Oxidation Mechanisms of Fiber-Textured AlTiTaN Coatings

The oxidation kinetics of AlTiTaN hard coatings deposited at 265 °C by DC magnetron sputtering were investigated between 700 and 950 °C for various durations. By combining dynamic secondary ion mass spectrometry (D-SIMS), X-ray diffraction (XRD), and transmission electron microscopy (TEM) investigations of the different oxidized coatings, we were able to highlight the oxidation mechanisms involved. The TEM cross-section observations combined with XRD analysis show that a single amorphous oxide layer comprising Ti, Al, and Ta formed at 700 °C. Above 750 °C, the oxide scale transforms into a bilayer oxide comprising an Al-rich upper oxide layer and a Ti/Ta-rich oxide layer at the interface with the coated nitride layer. From the D-SIMS analysis, it could be proposed that the oxidation mechanism was governed primarily by inward diffusion of O for temperatures of ≤700 °C, while at ≥750 °C, it is controlled by outward diffusion of Al and inward diffusion of O. Via a combination of structural and chemical analysis, it is possible to propose that crystallization of rutile lattice favors the outward diffusion of Al within the AlTiTa mixed oxide layer with an increase in the temperature of oxidation. The difference in the mechanisms of oxidation at 700 and 900 °C also influences the oxidation kinetics with respect to oxidation time. Formation of a protective alumina layer decreases the rate of oxidation at 900 °C for long durations of oxidation compared to 700 °C. Along with the oxidation behavior, the enhanced thermal stability of AlTiTaN compared to that of the TiAlN coating is illustrated.

Characterization of the Inhomogeneous Distribution of Light Elements in Ferritic Heat-Resistant Steels by Secondary Ion Mass Spectrometry

The addition of a small amount of boron and nitrogen is known to improve the creep strength and life of ferritic heat-resistant steels. These light elements are thought to be distributed in the microstructures in a complicated manner during the heat treatment and creep of these steels. In order to understand the influence of the light elements on the mechanical properties of ferritic heat-resistant steels, a microscopic distribution analysis of the light elements is of importance. In this study, two types of secondary ion mass spectrometry (SIMS) methods were used to investigate the measurement conditions for analyzing secondary ions derived from boron and nitrogen in steels. In dynamic SIMS with a quadrupole analyzer, boron in the samples was effectively detected as BO2– ions under irradiation with primary O2+ ions. From the time-of-flight (ToF) SIMS using a focused primary Bi32+ ion beam coupled with the exposure of the sample to a low partial pressure of oxygen, it was suggested that boron is enriched in M23C6 carbides in the steels and it may be, more or less, segregated at prior austenite grain boundaries with a moderate amount of nitrogen during normalizing. It was also demonstrated that nitrogen is precipitated as boron nitride in steels containing an excess amount of boron and nitrogen. The characteristics of the distribution of boron and nitrogen in the steels are discussed on the basis of the thermodynamic properties of these elements in the steels.

Transport parameters and optical properties of selectively doped Ga(Al)As/Zn(Mn)Se heterovalent structures with a two-dimensional hole channel

The growth of III–V/II–VI:Mn heterostructures with a high hole concentration in the AlGaAs:Be/GaAs/AlGaAs 2D channel situated in the immediate vicinity of the AlGaAs/Zn(Mn)Se heterovalent interface by molecular-beam epitaxy is reported. Despite the decrease in the hole concentration in the GaAs channel upon a decrease in the distance between the channel and the heterovalent interface, the hole concentration reaches a value of 1.5 × 1013 cm−2 at a temperature of 300 K even at the minimum distance of 1.2 nm. Deep profiling by dynamic secondary-ion mass spectrometry confirmed the back diffusion of Mn from ZnMnSe into the III–V part. High hole concentration and the presence of magnetic manganese ions in the GaAs conduction channel determine the interest in the structures as possible objects in which the effect of magnetic ordering in heterogeneous semiconductor systems can be studied.

Linking Vertical Bulk‐Heterojunction Composition and Transient Photocurrent Dynamics in Organic Solar Cells with Solution‐Processed MoOx Contact Layers

It is demonstrated that a combination of microsecond transient photocurrent measurements and film morphology characterization can be used to identify a charge‐carrier blocking layer within polymer:fullerene bulk‐heterojunction solar cells. Solution‐processed molybdenum oxide (s‐MoOx) interlayers are used to control the morphology of the bulk‐heterojunction. By selecting either a low‐ or high‐temperature annealing (70 °C or 150 °C) for the s‐MoOx layer, a well‐performing device is fabricated with an ideally interconnected, high‐efficiency morphology, or a device is fabricated in which the fullerene phase segregates near the hole extracting contact preventing efficient charge extraction. By probing the photocurrent dynamics of these two contrasting model systems as a function of excitation voltage and light intensity, the optoelectronic responses of the solar cells are correlated with the vertical phase composition of the polymer:fullerene active layer, which is known from dynamic secondary‐ion mass spectroscopy (DSIMS). Numerical simulations are used to verify and understand the experimental results. The result is a method to detect poor morphologies in operating organic solar cells.

Electrical Performance of Organic Solar Cells with Additive‐Assisted Vertical Phase Separation in the Photoactive Layer

Understanding the vertical phase separation of donor and acceptor compounds in organic photovoltaics is requisite for the control of charge transport behavior and the achievement of efficient charge collection. Here, the vertically phase‐separated morphologies of poly(3‐hexylthiophene):[6,6]phenyl‐C61‐butyric acid methyl ester (P3HT:PCBM) blend films are examined with transmission electron microtomography, dynamic secondary ion mass spectroscopy, and X‐ray photoelectron spectroscopy. The 3D morphologies of the processed films are analyzed and how the solvent additive causes vertical segregation is determined. The photocurrent–voltage characteristics of the vertically segregated blend films are strongly dependent on the 3D morphological organization of the donor and acceptor compounds in the photoactive layer. This dependence is correlated with asymmetric carrier transport at the buried interface and the air surface in the vertically segregated blend films.

Dynamics and Mechanism of Flame Retardants in Polymer Matrixes: Experiment and Simulation

We investigate the dynamics and the mechanism of flame retardants in polycarbonate matrixes to explore for a way of designing efficient and environment-friendly flame retardants. The high phosphorus content of organic phosphates has been considered as a requirement for efficient flame retardants. We show, however, that one can enhance the efficiency of flame retardants even with a relatively low phosphorus content by tuning the dynamics and the intermolecular interactions of flame retardants. This would enable one to design bulkier flame retardants that should be less volatile and less harmful in indoor environments. UL94 flammability tests indicate that even though the phosphorus content of 2,4-di-tert-butylphenyl diphenyl phosphate (DDP) is much smaller with two bulky tertiary butyl groups than that of triphenyl phosphate (TPP), DDP should be as efficient of a flame retardant as TPP, which is a widely used flame retardant. On the other hand, the 2-tert-butylphenyl diphenyl phosphate (2-tBuDP), with a lower phosphorus content than TPP but with a greater phosphorus content than DDP, is less efficient as a flame retardant than both DDP and TPP. Dynamic secondary ion mass spectrometry and molecular dynamics simulations reveal that the diffusion of DDP is slower by an order of magnitude at low temperature than that of TPP but becomes comparable to that of TPP at the ignition temperature. This implies that DDP should be much less volatile than TPP at low temperature, which is confirmed by thermogravimetric analysis. We also find from Fourier transform infrared spectroscopy that Fries rearrangement and char formation are suppressed more by DDP than by TPP. The low volatility and the suppressed char formation of DDP suggest that the enhanced flame retardancy of DDP should be attributed to its slow diffusivity at room temperature and yet sufficiently high diffusivity at high temperature.

Structural, morphological, and defect properties of metamorphic In0.7Ga0.3As/GaAs0.35Sb0.65 p-type tunnel field effect transistor structure grown by molecular beam epitaxy

Structural properties of metamorphic In0.7Ga0.3As/GaAs0.35Sb0.65 p-type tunnel field effect transistor (TFET) structure grown by molecular beam epitaxy were comprehensively investigated. High resolution x-ray diffraction revealed symmetric strain relaxation and pseudomorphic In0.7Ga0.3As/GaAs0.35Sb0.65 active layers with respect to the In0.7Al0.3As buffer, indicating a low dislocation density within the active region. The surface morphology of this structure exhibited a typical two-dimensional cross-hatch pattern with a low root-mean-square roughness of 2.58 nm. Cross-sectional transmission electron microscopy demonstrated a low threading dislocation density within the active region, suggesting high crystalline quality of this p-type TFET structure. Dynamic secondary ion mass spectrometry exhibited an abrupt doping profile over the In0.7Ga0.3As/GaAs0.35Sb0.65 source/channel junction as well as minimal level of intermixing between As and Sb atoms. Thus, these structural properties showed high quality of this structure and provided critical guidance for the fabrication of As/Sb based staggered gap complementary TFETs for ultra-low standby power and energy efficient logic applications.

Reversible room-temperature ferromagnetism in Nb-doped SrTiO3single crystals

The search for oxide-based room-temperature ferromagnetism has been one of the holy grails in condensed matter physics. Room-temperature ferromagnetism observed in Nb-doped SrTiO3 single crystals is reported in this Rapid Communication. The ferromagnetism can be eliminated by air annealing (making the samples predominantly diamagnetic) and can be recovered by subsequent vacuum annealing. The temperature dependence of magnetic moment resembles the temperature dependence of carrier density, indicating that the magnetism is closely related to the free carriers. Our results suggest that the ferromagnetism is induced by oxygen vacancies. In addition, hysteretic magnetoresistance was observed for magnetic field parallel to current, indicating that the magnetic moments are in the plane of the samples. The x-ray photoemission spectroscopy, the static time-of-flight and the dynamic secondary ion mass spectroscopy and proton induced x-ray emission measurements were performed to examine magnetic impurities, showing that the observed ferromagnetism is unlikely due to any magnetic contaminant.

Plasma polymerization of C4Cl6 and C2H2Cl4 at atmospheric pressure

In the present study, the feasibility of synthesizing chlorinated films by a dielectric barrier discharge at atmospheric pressure is assessed. Two different liquid monomers (hexachlorobuta-1,3-diene C4Cl6 and 1,1,1,2-tetrachloroethane C2H2Cl4) are tested and results show that organic coatings rich in chlorine can be deposited. The correlation and complementarity of water contact angle, X-ray photoelectron spectroscopy, secondary ion mass spectrometry and ellipsometry techniques have provided information to compare the properties of the perchlorinated layers built up from monomers with different Cl/C ratios and hydrogen concentrations. The bond dissociation energies of C–Cl2, C–Cl and C–C/CC/C–H are used to provide an explanation for the differences in films structure recorded by X-ray photoelectron spectroscopy and secondary ion mass spectrometry. Finally, dynamic-secondary ion mass spectrometry complemented by ellipsometry is used to calculate a deposition rate ranging from 40 to 70 nm/min depending on the plasma conditions. These measurements also show a good homogeneity of the film throughout its thickness.

Dynamic SIMS Analysis of PEMFC Catalyst Layer/Solid Electrolyte Interfaces

Cobalt polypyrrole-supported carbon (CoPPy/C) has been expected to be a low-cost alternative to platinum catalysts for proton exchange membrane fuel cell (PEMFC) cathode. Although the catalytic activity of the CoPPy/C is relatively high, improvement of the durability to long-term use is still challenging problem. In order to know the deterioration mechanism of PEMFC cathode, dynamic-secondary ion mass spectrometry (D-SIMS) was used in this study for analysis of cathode catalyst layer/solid electrolyte membrane interfaces before and after an aging test. The depth profile of cobalt species across the interface of a CoPPy/C cathode was significantly changed after the aging test. From the depth profile of cobalt in the CoPPy/C catalyst, it is suggested that the cobalt species may transfer in the membrane along with the flow of the back diffusion water.

Latent Cracking of Tantalum-Titanium Welds Due to Hydrogen Embrittlement

Establishing electrical interconnects in implantable electronic medical devices frequently requires joining of dissimilar materials. A weld between a tantalum wire and titanium sheet metal on a contact module is presented as an example for dissimilar joining. Latent, brittle cracking was observed in the proximity of the weld upon pull testing. The weld cracking occurs by the mechanism known as hydrogen stress cracking (HSC) and is due to titanium hydride formation. Diffusion facilitated hydrogen transport into the weld area. Diffusing hydrogen accumulates preferably in regions of high stress, causing latent titanium hydride formation and embrittlement of the weld. A broad array of analytical tools such as scanning electron microscopy (SEM), transmission electron microscopy, electron backscattered diffraction, dynamic secondary ion mass spectroscopy, and nanoindentation were utilized to identify the root cause for HSC.

50nm-Scale Localization of Single Unmodified, Isotopically Enriched, Proteins in Cells

Imaging single proteins within cells is challenging if the possibility of artefacts due to tagging or to recognition by antibodies is to be avoided. It is generally believed that the biological properties of proteins remain unaltered when 14N isotopes are replaced with 15N. 15N-enriched proteins can be localised by dynamic Secondary Ion Mass Spectrometry (D-SIMS). We describe here a novel imaging analysis algorithm to detect a few 15N-enriched proteins - and even a single protein - within a cell using D-SIMS. The algorithm distinguishes statistically between a low local increase in 15N isotopic fraction due to an enriched protein and a stochastic increase due to the background. To determine the number of enriched proteins responsible for the increase in the isotopic fraction, we use sequential D-SIMS images in which we compare the measured isotopic fractions to those expected if 1, 2 or more enriched proteins are present. The number of enriched proteins is the one that gives the best fit between the measured and the expected values. We used our method to localise 15N-enriched thymine DNA glycosylase (TDG) and retinoid X receptor α (RXRα) proteins delivered to COS-7 cells. We show that both a single TDG and a single RXRα can be detected. After 4 h incubation, both proteins were found mainly in the nucleus; RXRα as a monomer or dimer and TDG only as a monomer. After 7 h, RXRα was found in the nucleus as a monomer, dimer or tetramer, whilst TDG was no longer in the nucleus and instead formed clusters in the cytoplasm. After 24 h, RXRα formed clusters in the cytoplasm, and TDG was no longer detectable. In conclusion, single unmodified proteins in cells can be counted and localised with 50 nm resolution by combining D-SIMS with our method of analysis.