Infrared Transparency Research Articles

Characterization of MoS2:Nb sputtered thin films. An application as hole transport layer in Cu2ZnSnS4/Si tandem solar cells

MoS2:Nb films deposited by radio-frequency magnetron sputtering are investigated in view of their application in infrared (IR)-transparent contacts for tandem photovoltaic devices.This material is already known to give a good electrical contact with p-type chalcogenide semiconductors, which are typically grown onto opaque molybdenum metallic contacts and a MoS2 layer spontaneously forms at the back interface during the on-top semiconductor growth. Our study explores a different approach, which involves the direct growth of IR-transparent MoS2:Nb films via sputtering inside complete photovoltaic devices, like Cu2ZnSnS4 (CZTS)-based single junction solar cells and CZTS/Si tandem devices. Films deposited at different sputtering pressures are compared by analysing their microstructure, morphology, chemical composition, optical and electrical properties. The effects of post-deposition sulfurization treatments are also investigated. We find that MoS2:Nb films deposited at around 0.1 Pa exhibit compactness but show a notable sulfur deficit ([S]/[Mo]≈1.4), a significant sub-bandgap optical absorptance and lack of crystallinity. Increasing the Ar pressure to 1 Pa raises the [S]/[Mo] ratio to 2.2, yielding crystalline films with good IR-transparency, although with a porous morphology. Despite 0.5 wt% Nb-doping of the sputtering target, the as-deposited films demonstrate n-type conductivity likely due to uncontrolled impurities and intrinsic defects. Ultraviolet Photoemission Spectroscopy measurements suggest that films’ work function higher than 5 eV can be obtained with a post-deposition sulfurization, making these materials suitable as Hole Transport Layer in photovoltaic applications. A similar increase in work function is expected in the CZTS/MoS2 junctions, since the sputtered MoS2:Nb films undergo a sulfurization process needed to obtain the overlying polycrystalline CZTS absorber.CZTS solar cells produced with sputtered MoS2 and Transparent Conductive Oxides contacts on glass substrates, despite plagued by severe adhesion problems, show the potentiality to give efficiencies comparable to reference devices with standard Mo back contact. Fabrication of CZTS/Si tandem devices on textured silicon bottom cells yields a maximum efficiency of 4.4 %, primarily hindered by the low quality of the CZTS film on textured substrates. Nonetheless, optoelectronic characterizations based on both spectrophotometric and quantum efficiency measurements confirm a good IR transparency of the MoS2-based intermediate contacts and the desired electrical behaviour.

Elevating high-temperature insulation performance of silica aerogels enabled by innovative surface-structured opacifiers

Silica aerogel, recognized as an exceptional material for thermal insulation, has gained considerable attention in thermal protection. However, its inherent infrared transparency compromises its insulating performance at high temperatures. To address this limitation, incorporating micron-sized opacifier particles has emerged as a crucial strategy. This study introduces a novel opacifier particle, distinguished by surface protrusions inspired by the ’structural absorption’ mechanism, and assesses its extinction capabilities. Then, a thorough analysis was conducted to understand how the shape, volume, and numbers of these surface protrusions influence the radiative heat transfer properties of silica aerogels. The findings reveal that the presence of protrusions on the opacifier surface significantly enhances its extinction capacity, consequently reducing the radiative thermal conductivity of silica aerogels. Notably, cylindrical protrusions demonstrate the most effective extinction properties compared to spherical protrusions and rectangular protrusions. Additionally, for opacifier particles with cylindrical protrusions, there exists an optimal number of 12 protrusions that minimize the radiative thermal conductivity of the aerogel. At 1300 K, the radiative thermal conductivity of the silica aerogel doped with opacifiers featuring 12 protrusions is 22.6 % lower than that of the silica aerogel doped with opacifiers lacking protrusions. Moreover, it was observed that maintaining a constant diameter of cylindrical protrusions while increasing their height diminishes the radiative thermal conductivity of silica aerogel. However, the effect on the radiative thermal conductivity becomes less significant beyond a certain protrusion height. The outcomes of this study provide significant insights into the innovation of opacifiers.

Fundamental optical constants and anti-reflection coating of melt-grown, polished CsPbBr3 crystals

AbstractLead halide perovskites are notorious for water-sensitivity and low hardness. Consequently, polishing CsPbBr3 crystals to achieve high-quality surfaces is challenging. We present a breakthrough mechanical polishing methodology tailored to the specific needs of these soft, moisture-sensitive semiconductors. Three-dimensional optical surface profiles over ~ 1 mm2 areas demonstrate high-quality surfaces with root-mean-square roughness values (< 10 nm) that are unparalleled for melt-grown CsPbBr3. We additionally delve into the polished wafers’ fundamental optical constants and introduce an anti-reflection coating method, setting new standards for short-wave infrared transparency in CsPbBr3. These pivotal processing guidelines pave the way for advancing halide perovskite applications beyond academic curiosity. Graphical abstract

EuSi7P10: An Inorganic Supramolecular Nonlinear Optical Crystal Exhibiting Strong Second-Harmonic Generation Response.

Inorganic supramolecular compounds are the emergent class of infrared (IR) nonlinear optical (NLO) materials. However, the reported inorganic supramolecular IR NLO pnictides are still scarce. In this work, a new inorganic supramolecular IR NLO phosphide, EuSi7P10, has been synthesized using the metal salt flux method. The structure of EuSi7P10 features an anionic host framework containing the oriented [Si7P16] dual-T2 supertetrahedra with the guest Eu2+ cations filling in the intervals. Additionally, EuSi7P10 exhibits strong phase-matched (PM) second-harmonic generation (SHG) (4.0 × AgGaS2), large birefringence (0.087 @2050 nm), and wide infrared transparency. This study highlights the potential of inorganic supramolecular pnictides for exploring high-performance IR NLO crystals.

The "energy gap law" for mid-infrared nanocrystals.

Colloidal quantum dots are of increasing interest for mid-infrared detection and emission, but device performances will vastly benefit from reducing the non-radiative recombination. Empirically, the photoluminescence quantum yield decreases exponentially toward the mid-infrared, which appears similar to the energy gap law known for molecular fluorescence in the near-infrared. For molecules, the mechanism is electron-vibration coupling and fast internal vibrational relaxation. Here, we explore the possible mechanisms for inorganic quantum dots. The primary mechanism is assigned to an electric dipole near-field energy transfer from the quantum dot electronic transitions to the infrared absorption of surface organic ligands and then to the multiphonon absorption of the quantum dot inorganic core or the surrounding inorganic matrix. In order to obtain luminescent quantum dots in the 3-10μm range, we motivate the importance of using inorganic matrices, which have a higher infrared transparency compared to organic materials. At longer wavelengths, inter-quantum dot energy transfer is noted to be much faster than radiative relaxation, indicating that bright mid-infrared colloidal quantum dot films might then benefit from dilution.

Correlation between composition, structure, and acousto-optic properties of As100-xSx chalcogenide glasses

Acousto-optic (AO) devices have great application potential in laser technology and network communication. Chalcogenide (ChG) glass is promising for AO devices because of its excellent infrared transparency and high AO figure of merit. Among them, As–S glasses represent the most typical and extensively studied ChG system. However, the correlation between the network structure of As–S glasses in the As-rich and S-rich regions and their AO properties remains to be investigated. In this work, the effect of glass composition and glass structure on the AO properties of As–S glasses was investigated. The gradual formation of homopolar As–As and S–S bonds leads to the weakening of the network crosslinking degree of the glass structure in the vicinity of As-rich and S-rich regions, which results in a reduction in the AO properties. In particular, the presence of long-chain As–S–As bonds in the As40S60 glass primarily causes its superior AO properties. The above results provide an important reference for the further investigation on the correlation between glass composition, structure, and AO properties and the development of As–S based AO media and devices.

Facile preparation of infrared-transparent, superhydrophobic coatings for infrared detection and personal thermal management

Capturing thermal radiation using highly infrared (IR)-transparent materials have drawn great attention for diverse applications, such as IR guidance, IR detection, thermal radiation imaging, radiative cooling etc. However, the previously reported IR-transparent materials have the bottleneck of lacking superhydrophobicity, resulting in the degradation due to the dust, fog, rain, frost outdoors. Here, a durable IR-transparent superhydrophobic coating is reported via the spraying of polyester (PE) microspheres and fluorinated ZnS nanoparticles (NPs). Due to the high transmittance of ZnS and PE, the coating shows excellent IR transparency (around 90 %) in 8 ∼ 14 μm thermal IR band. Benefitting from the robustness of 3D connected PE network, the coating maintains superhydrophobicity after 180 cycles of linear wearing under 6 kPa. Moreover, the water jetting/atomizing/dust tests indicate that this coating effectively ensures the high accuracy of IR imaging lens under rainy/foggy/dusty environments. This coating on fabrics also achieves a remarkable radiative cooling effect for outdoor conditions to keep human body comfortable. With its facile preparation and versatile features, this coating has great potential on IR window, IR imaging and personal thermal management.

Customized linear refractive index GRIN prepared by rapid sintering of multilayer chalcogenide glass powders

AbstractGradient refractive index (GRIN) lenses have recently become a hot topic in compact imaging and achromaticity. Current research focuses on exploiting GRIN materials and upgrading the preparation technology. In this study, infrared (IR) GRIN materials were successfully prepared by spark plasma sintering of multilayer chalcogenide glass (ChGs) powders. ChGs powders were derived from the Ge20Se80‐xTex series glasses (x = 0–28 mol%) with a maximum refractive index difference (Δn) of 0.25. The similar glass transition temperatures (ΔTg < 10°C) promote efficient sintering of multilayer powders. Six‐, eight‐, and ten‐layer powders of different compositions were rapidly sintered with a thickness of 600, 300, and 200 µm per layer, respectively. Such tiny layer thickness enables the GRIN materials to exhibit nearly linear refractive index variation. Energy dispersive spectroscopy line scans well characterized the gradient variation of GRIN. The maximum deviation of the refractive index gradient from the fitted target line was only ± 0.016 for the 10‐layer GRIN. The sintered GRIN shows excellent IR transparency, which is of great interest for mid‐wave and long‐wave infrared imaging.

Radiative cooling textiles using industry-standard particle-free nonporous micro-structured fibers

Abstract Thermal radiation is a major dissipative pathway for heat generated by the human body and offers a significant thermoregulation mechanism over a wide range of conditions. We could use this in garment design to enhance personal cooling, which can improve the wearing comfort of garments or even result in energy savings in buildings. At present, however, radiative cooling has received insufficient attention in commercial design and production of textiles for wearable garments. Textiles that efficiently transmit the radiative heat were recently demonstrated, but either do not utilize standard weaving and knitting processes for wearable garments or require substantial process modifications. Here, we demonstrate the design and implementation of large-scale radiative cooling textiles for localized cooling management and enhanced thermal comfort using industry-standard particle-free nonporous micro-structured fibers that are fully compatible with standard textile materials and production methods. The micro-structured fibers, yarns and fabrics are part of a hierarchical photonic structure design that renders the textiles highly infrared transparent (up to > 0.8) while assuring visual opacity (up to 0.99). We design radiative cooling textiles with first-principles electromagnetic methods and fabricate them using commercial textile materials and formation facilities. Our “fabless” approach is confirmed by very good quantitative agreement between design and measurements. The resulting fabrics exhibit wearability properties expected of wearable textiles, and lower skin temperature by ≥ 3 °C compared to conventional textiles, which offers the potential for > 30 % energy savings in buildings and increases wearing comfort by significantly reducing the reliance on latent heat dissipation for thermoregulation.

(Invited) Novel Plasmonic Materials as Fluorescence Enhancers for Biosensing and Bioimaging in Near Infrared Window

Novel plasmonic nanostructures, which are near-IR active, has been developed in our group as powerful fluorescence enhancers. The technology is highly versatile for ultrasensitive diagnosis and deep tissue imaging-two key areas for future diagnostics. I will present some nanostructures we have designed and developed and then discuss their applications in biosensing and cell imaging in near infrared biological transparency window.

ACu4AsS4 (A = K, Rb): Two infrared nonlinear optical crystals with strong second-harmonic generation responses originating from multiple chromophores

Infrared (IR) nonlinear optical (NLO) crystals are of great significance in modern laser technology, and metal chalcogenides are receiving increasing interest as promising IR NLO candidates. To explore new IR NLO materials with enhanced properties, two quaternary chalcogenides with multiple chromophores, KCu4AsS4 and RbCu4AsS4, were synthesized using the solvothermal method. KCu4AsS4 and RbCu4AsS4 feature 2D [Cu6As2S6]∞ anionic layers with multiple chromophores, and exhibit strong phase-matched second-harmonic generation (SHG) responses (1.8–2.0 × AgGaS2), wide band gaps, suitable birefringence (0.083 and 0.074 @ 2050 nm) and wide infrared transparency. The theoretical calculation results suggest that the strong SHG responses are ascribed to the 2D [Cu6As2S6]∞ anionic layers.

A flexible electrochromic device with variable infrared emissivity based on W18O49 nanowire cathode and MXene infrared transparent conducting electrode

Electrochromism with tunable infrared (IR) responses has emerged as an intriguing technology for adaptive IR camouflage and radiative thermal management. Its current development is however hindered by low IR emissivity modulation and unsatisfactory cycle life. Herein, a flexible IR electrochromic device with large IR emissivity modulation and high stability is fabricated by combining an oxygen-deficient W18O49 nanowire cathode and a MXene-based IR transparent conducting electrode. The nanowire structure and abundant oxygen vacancies of W18O49 works in synergy with the high IR transparence of the MXene conducing electrode, to provide the IR emissivity to vary from 0.8 to 0.4 within 3–5 μm (△ε = 0.4), and from 0.77 to 0.3 within 8–14 μm (△ε = 0.47). A long cycle life of more than 2000 cycles was also verified, which could be attributed to the high stability of W18O49 and no material phase transition during cycling. This work demonstrates a viable pathway to design and build high performance flexible IR electrochromic devices for adaptive thermal management.

Fabrication of Plastic Optics from Chalcogenide Hybrid Inorganic/Organic Polymers for Infrared Thermal Imaging

AbstractThe development of infrared (IR) plastic optics for infrared thermal imaging, particularly, in the long‐wave IR (LWIR) spectrum (7–14 µm) is an area of growing technological interest due to the potential advantages associated with plastic optics (e.g., moldability and low cost). The development of a new class of optical polymers, chalcogenide‐based inorganic/organic hybrid polymers (CHIPs) derived from the inverse vulcanization of elemental sulfur, has enabled significant improvements in IR transparency due to reduction of IR absorbing organic comonomer units. The vast majority of effort has focused on new chalcogenide hybrid polymer synthesis and optical property improvements (e.g., refractive index, Abbe number, and LWIR transmission); however, fabrication and IR imaging methodology to prepare optical components has not been demonstrated, which remains critical to develop viable IR plastic optics. A new methodology is reported to fabricate optical components and evaluate LWIR imaging performance of this emerging class of optical polymers. New diffractive flat optics with a Fresnel lens design for these materials have been developed, along with a basic LWIR imaging system to evaluate CHIPs for LWIR imaging. This system‐based approach enables correspondence of copolymer structure‐property correlations with LWIR imaging performance, along with demonstration of room temperature LWIR imaging.

Breaking through the plasma wavelength barrier to extend the transparency range of ultrathin indium tin oxide films into the far infrared

Indium tin oxide (ITO) film, which is the most commonly used transparent conductive film (TCF), has traditionally been believed to be transparent in the visible spectrum but to reflect infrared (IR) light beyond the plasma wavelength (λp). However, our theoretical analysis challenges this notion by demonstrating that an ultrathin ITO TCF that is thinner than the light's penetration depth can overcome the transmission barrier at λp. To validate the theoretical modeling, we have successfully fabricated ultrathin ITO films that, despite having λp ≈ 1 μm, remain transparent from 400 nm to 20 μm. This represents the broadest transparency range ever reported for any In2O3-based TCF. The 10-nm-thick ITO TCFs have high visible transmittance (91.0% at 550 nm), low resistivity (5 × 10−4 Ω cm), and good IR transmittance (averaging 60% over 1.35–18.35 μm). Their IR transparency facilitates radiative cooling of the underlying circuitry. When an operational resistor is enclosed by commercial ITO TCFs that are 140 nm thick, its temperature increases. However, using 10-nm-thick ITO TCFs instead of the commercial ones can completely avoid this temperature rise. Moreover, attaching a silver grid to a 10-nm-thick ITO TCF can reduce the effective sheet resistance to ∼10 Ω/□ at the expense of only ∼3% transmittance. This development paves the way for large-scale applications that require low sheet resistance and far-IR transparency.

Multicolored Displays with Selective Visible‐Infrared Spectral Modulation for Optical Information Transmission

AbstractPolyaniline (PANI) can achieve reversible optical modulation in visible and infrared (IR) bands under the action of voltage. However, PANI‐based electrochromic devices cannot cope with the dual detection of visible and IR light to realize the transmission of information due to the linkage restriction between the spectral modulation in the visible and IR region. Here, IR low‐absorptive inorganic pigments as colorants and IR high‐transparent polymer as a binder are utilized to prepare colored films with high transparency. A camouflage layer against visible light detection is constructed on the surface of IR electrochromic devices, and the information transmission is realized in the IR band by controlling the thermal radiation characteristics. Furthermore, thermochromic microcapsules (TMs) that change color under external thermal stimuli are introduced to fabricate a thermochromic and IR transparent functional layer, which is attached to the surface of IR electrochromic devices and endows the devices with separate spectral modulation ability in the visible and IR region. Multicolored displays are fabricated by arraying various devices. Moreover, visual patterns are prepared on the surface of IR electrochromic devices by dispensing technology. This configuration endows the device with a promising potential for anti‐counterfeiting, optical security, and related applications.

Visible and infrared transparent conductive films with passive cooling capabilities

In order to facilitate radiative cooling in optoelectronic devices, it is necessary to employ infrared (IR) transparent conductive films (TCFs) that permit thermal radiation from internal circuits to pass through. This can be accomplished by using TCFs with a wide transparency range that extends into the far-IR spectrum. We have produced hafnium-doped indium oxide (InHfO) TCFs that have a wide transparency range spanning from 400 nm to 20 μm. These TCFs, with a thickness of 120 nm, exhibit a sheet resistance of approximately 200 Ω/□, high visible relative transmittance (90% at 550 nm, comparable to ITO), and IR transparency (66.9% in the 1.35–20 μm range). By replacing commercial ITO TCFs with InHfO TCFs, we successfully decreased the operating temperature of an enclosed resistor from 65.5 °C to 63.6 °C, and potentially to 61.1 °C via radiative cooling. This decrease corresponds to around 5–10% of the temperature difference between the resistor and room temperature. The InHfO TCFs we have prepared are suitable for a range of applications requiring transparency from the visible to the far-IR spectrum and may open up new avenues for optoelectronic applications.

Long-wave infrared transparent sulfur polymers enabled by symmetric thiol cross-linker

Infrared (IR) transmissive polymeric materials for optical elements require a balance between their optical properties, including refractive index (n) and IR transparency, and thermal properties such as glass transition temperature (Tg). Achieving both a high refractive index (n) and IR transparency in polymer materials is a very difficult challenge. In particular, there are significant complexities and considerations to obtaining organic materials that transmit in the long-wave infrared (LWIR) region, because of high optical losses due to the IR absorption of the organic molecules. Our differentiated strategy to extend the frontiers of LWIR transparency is to reduce the IR absorption of the organic moieties. The proposed approach synthesized a sulfur copolymer via the inverse vulcanization of 1,3,5-benzenetrithiol (BTT), which has a relatively simple IR absorption because of its symmetric structure, and elemental sulfur, which is mostly IR inactive. This strategy resulted in approximately 1 mm thick windows with an ultrahigh refractive index (nav > 1.9) and high mid−wave infrared (MWIR) and LWIR transmission, without any significant decline in thermal properties. Furthermore, we demonstrated that our IR transmissive material was sufficiently competitive with widely used optical inorganic and polymeric materials.

Cover Picture: Near‐Infrared Fluorescence Lifetime Imaging of Biomolecules with Carbon Nanotubes (Angew. Chem. Int. Ed. 24/2023)

Fluorescence lifetime imaging is a powerful technique. In their Research Article (e202300682), Sebastian Kruss et al. used single-walled carbon nanotubes (SWCNTs) as fluorescent probes/sensors for biomolecules in the near infrared (NIR) tissue transparency window. The SWCNTs were functionalized with DNA to render them selective for the important neurotransmitter dopamine. Time correlated single photon counting in a confocal microscope was used to read out fluorescence lifetime, which changed with dopamine concentration. This approach enabled the measurement of dopamine around cells. Thus, the fluorescence lifetime of SWCNTs becomes a new sensing strategy for bio(molecules).

Titelbild: Nahinfrarot Fluoreszenz‐Lebensdauer Mikroskopie von Biomolekülen mit Kohlenstoffnanoröhren (Angew. Chem. 24/2023)

Fluorescence lifetime imaging is a powerful technique. In their Research Article (e202300682), Sebastian Kruss et al. used single-walled carbon nanotubes (SWCNTs) as fluorescent probes/sensors for biomolecules in the near infrared (NIR) tissue transparency window. The SWCNTs were functionalized with DNA to render them selective for the important neurotransmitter dopamine. Time correlated single photon counting in a confocal microscope was used to read out fluorescence lifetime, which changed with dopamine concentration. This approach enabled the measurement of dopamine around cells. Thus, the fluorescence lifetime of SWCNTs becomes a new sensing strategy for bio(molecules).

Enhanced infrared transmittance by modulation of electrical and optical properties of Sm-doped SnO2 thin films

Although metal oxides exhibit high electrical conductivity and high transparency in the visible wavelength range, they suffer from low transmittance in the infrared (IR) spectral range. This paper reports the deposition of Sm-doped SnO2 thin films with high IR transparency by modulating the electrical and optical properties. The Sm-doped SnO2 thin films grown by spray pyrolysis showed a directional columnar structure and a change in crystal structure from tetragonal to orthorhombic with increasing Sm doping content. The undoped SnO2 thin film exhibited intrinsic n-type conductivity with a high background charge carrier concentration, which resulted in low IR transmittance of <20%. As the Sm doping content increased, the charge carrier concentration decreased drastically, resulting in an increase in IR transmittance of SnO2 thin films from 18.8 to 85.2%. The Sm element acted a critical role in controlling the electrical and optical properties of SnO2 thin films by acting as a reducing agent and dopant.