Frequency-domain Thermoreflectance Research Articles

Assessing thermal resistance in fusion bond layers of 3D heterogeneous electronics packaging

We investigated thermal management challenges in semiconductor devices that use fusion bonding, with a focus on measuring the thermal resistance of the bonded interface. Starting with two fusion-bonded silicon wafers, we thinned the top wafer to below 100 μm and used frequency domain thermoreflectance to measure the effective thermal boundary resistance of the fusion bond. We established the measurement uncertainty with a multilayer thermal diffusion model, considering the effects of the top Si layer thickness and laser spot size. The thermal boundary resistance was measured to be 0.2 and 0.5 m2K/MW for two types of bonded wafers, with total SiO2 film thicknesses of 200 and 470 nm at the fusion bond layer, respectively. We also created defects at the interface and imaged these defects with the thermal phase response at specific frequencies chosen according to a thermal model. The method described can be applied to other types of wafer-to-wafer or die-to-die bonding including direct, polymeric, and metallic bonds.

An instrumentation guide to measuring thermal conductivity using frequency domain thermoreflectance (FDTR).

Frequency Domain Thermoreflectance (FDTR) is a versatile technique used to measure the thermal properties of thin films, multilayer stacks, and interfaces that govern the performance and thermal management in semiconductor microelectronics. Reliable thermal property measurements at these length scales (≈10nm to ≈10μm), where the physics of thermal transport and phonon scattering at interfaces both grow in complexity, are increasingly relevant as electronic components continue to shrink. While FDTR is a promising technique, FDTR instruments are generally home-built; they can be difficult to construct, align, and maintain, especially for the novice. Our goal here is to provide a practical resource beyond theory that increases the accessibility, replicability, and widespread adoption of FDTR instrumentation. We provide a detailed account of unpublished insights and institutional knowledge that are critical for obtaining accurate and repeatable measurements of thermal properties using FDTR. We discuss component selection and placement, alignment procedures, data collection parameters, common challenges, and our efforts to increase measurement automation. In FDTR, the unknown thermal properties are fit by minimizing the error between the phase lag at each frequency and the multilayer diffusive thermal model solution. For data fitting and uncertainty analysis, we compare common numerical integration methods, and we compare multiple approaches for fitting and uncertainty analysis, including Monte Carlo simulation, to demonstrate their reliability and relative speed. The instrument is validated with substrates of known thermal properties over a wide range of isotropic thermal conductivities, including Borofloat silica, quartz, sapphire, and silicon.

Semi-in-situ thermal transport characterization of thermal interface materials through a low-frequency thermoreflectance technique

Thermal transport characterization of thermal interface materials (TIMs), especially in their application scenario is so far challenging. Herein, we demonstrate a low-frequency frequency domain thermoreflectance technique to measure the semi-in-situ thermal transport properties of TIMs in a sandwiched structure. The measurement ability is first demonstrated by accurate measurement on several well-known materials. Then the thermal conductivity and interface thermal resistance of a thermal gel, a thermal pad composed of phase change materials and an Indium foil, sandwiched in two silicon slides are investigated. Sensitivity analysis emphasized the importance of pump laser spot size and modulation frequency in the measurement. For TIMs with low thermal conductivity, the sensitivity to interface thermal resistance is highly suppressed, while for TIMs with high thermal conductivity, the sensitivity to interface thermal resistance is prominent, which makes it easier to separately determine the TIM thermal conductivity and interface thermal resistance.

Measurements of Thermal Resistance Across Buried Interfaces with Frequency-Domain Thermoreflectance and Microscale Confinement.

Confined geometries are used to increase measurement sensitivity to thermal boundary resistance at buried SiO2 interfaces with frequency-domain thermoreflectance (FDTR). We show that radial confinement of the transducer film and additional underlying material layers prevents heat from spreading and increases the thermal penetration depth of the thermal wave. Parametric analyses are performed with finite element methods and used to examine the extent to which the thermal penetration depth increases as a function of a material's effective thermal resistance and the degree of material confinement relative to the pump beam diameter. To our surprise, results suggest that the measurement technique is not always the most sensitive to the largest thermal resistor in a multilayer material. We also find that increasing the degree to which a material is confined improves measurement sensitivity to the thermal resistance across material interfaces that are buried 10s of μm to mm below the surface. These results are used to design experimental measurements of etched, 200 nm thick SiO2 films deposited on Al2O3 substrates, and offer an opportunity for thermal scientists and engineers to characterize the thermal resistance across a broader range of material interfaces within electronic device architectures that have historically been difficult to access via experiment.

Seeking non-Fourier heat transfer with ultrabroad band thermoreflectance spectroscopy

Studying superdiffusive thermal transport is crucial for advanced thermal management in electronics and nanotechnology, ensuring devices run efficiently and reliably. Such study also contributes to the design of high-performance thermoelectric materials and devices, thereby improving energy efficiency. This work leads to a better understanding of fundamental physics and non-equilibrium phenomena, fostering innovations in numerous scientific and engineering fields. We are showing, from a one shot experiment, that clear deviations from classical Fourier behavior are observed in a semiconductor alloy such as InGaAs. These deviations are a signature of the competition that takes place between ballistic and diffusive heat transfers. Thermal propagation is modelled by a truncated Lévy model. This approach is used to analyze this ballistic-diffusive transition and to determine the thermal properties of InGaAs. The experimental part of this work is based on a combination of time-domain and frequency-domain thermoreflectance methods with an extended bandwidth ranging from a few kHz to 100 GHz. This unique wide-bandwidth configuration allows a clear distinction between Fourier diffusive and non-Fourier superdiffusive heat propagation in semiconductor materials. For diffusive processes, we also demonstrate our ability to simultaneously measure the thermal conductivity, heat capacity and interface thermal resistance of several materials over 3 decades of thermal conductivity.

Au ion irradiation induces ultralow thermal conductivity in GaN

Gallium nitride (GaN) is widely considered as a crucial semiconductor for the nuclear industry and space explorations due to its superior radiation hardness. Despite extensive studies of the electronic and optical properties of irradiated GaN, the effects of particle irradiation on the thermal properties remain largely unexplored. Here, we begin with single-crystalline GaN and employ an accelerator equipped with heavy gold ions (Au2+) as the radiation source in order to imitate extreme environments and maximize lattice damages. Eight different irradiated samples are prepared with the fluence of Au2+ spanning four orders of magnitude from 1011 to 1015 cm−2. The thermal conductivity (κ) of the ion-affected regions is measured using the laser pump–probe technique of frequency-domain thermoreflectance. We find that κ decreased consistently and notably with increasing irradiation fluence and observe a transition from crystal to glass-like thermal transport. Remarkably, the room-temperature κ of the GaN sample with the highest Au2+ fluence of 1 × 1015 cm−2 reaches about 1 Wm−1 K−1, which is two orders of magnitude lower than the κ of pristine GaN and approaches the theoretical minimum. A Callaway-type model captures the phonon–point defect scattering in samples with relatively low ion fluences. At higher fluences, the increased defect types and densities, together with the formation of nitrogen bubbles, further suppress phonon transport. Our findings are instrumental in fundamentally understanding the impact of heavy-ion irradiation on thermal transport and may prove useful for the application of GaN-based devices in radiation-intense environments.

Simultaneous determination of the phase boundary thermal resistance and thermal conductivity in phase-separated TiO2 thin films

Phase boundaries, most often between crystalline and amorphous phases of a material, are ubiquitous lattice imperfections in thin films, particularly deposited by low temperature processes such as atomic layer deposition (ALD). Thermal resistances from these boundaries may impede phonon transport and reduce thermal conductivity. However, to date, there have been no reports on the direct measurement of the phase boundary thermal resistance, due in part to challenges associated with fabricating an atomically flat yet geometrically planar interface between different phases within a film. Here, we present a systematic study to simultaneously determine the phase boundary thermal resistance and thermal conductivity in a series of phase-separated titanium oxide (TiO2) thin films prepared via plasma-enhanced ALD (PEALD). A precise implementation of per-cycle plasma treatment enables extremely localized crystallization—i.e., plasma-assisted atomic layer annealing (ALA)—and the fabrication of crystalline/amorphous layered structures with their respective thicknesses systematically varied. Frequency-domain thermoreflectance measures the effective thermal conductivity of each film and its top and bottom interfaces, confirmed independently using time-domain thermoreflectance. We simultaneously solve a system of linear equations generated by applying a series resistor model to each film, yielding the phase boundary thermal resistance of 5.1 m2 K GW–1 between crystalline and amorphous TiO2, as well as the thermal conductivities of 5.1 and 2.1 W m–1 K–1 for crystalline and amorphous TiO2, respectively. The results suggest that the crystalline/amorphous phase boundary acts like a layer of crystalline (amorphous) TiO2 with equivalent thickness ∼26 (∼11) nm.

Simultaneous Measurement of Thermal Conductivity and Volumetric Heat Capacity of Thermal Interface Materials Using Thermoreflectance.

Thermal interface materials are crucial to minimize the thermal resistance between a semiconductor device and a heat sink, especially for high-power electronic devices, which are susceptible to self-heating-induced failures. The effectiveness of these interface materials depends on their low thermal contact resistance coupled with high thermal conductivity. Various characterization techniques are used to determine the thermal properties of the thermal interface materials. However, their bulk or free-standing thermal properties are typically assessed rather than their thermal performance when applied as a thin layer in real application. In this study, we introduce a low-frequency range frequency domain thermoreflectance method that can measure the effective thermal conductivity and volumetric heat capacity of thermal interface materials simultaneously in situ, illustrated on silver-filled thermal interface material samples, offering a distinct advantage over traditional techniques such as ASTM D5470. Monte Carlo fitting is used to quantify the thermal conductivities and heat capacities and their uncertainties, which are compared to a more efficient least-squares method.

Multiscale phonon thermal transport in nano-porous silicon

We performed a comprehensive multi-scale phonon-mediated thermal transport study of nano-porous silicon (np-Si) films with average porosities in the range of φ = 30%–70%. This depth-resolved thermal characterization involves a combination of optical methods, including femtosecond laser-based time-domain thermo-reflectance (TDTR) with MHz modulation rates, opto-thermal micro-Raman spectroscopy, and continuum laser wave-based frequency domain thermo-reflectance (FDTR) with kHz modulation rates probing depths of studied samples over 0.5–1.2, 2–3.2, and 23–34 μm, respectively. We revealed a systematic decrease in thermal conductivity (k) with the rise of φ, i.e., with the lowering of the Si crystalline phase volumetric fraction. These data were used to validate our semi-classical phonon Monte Carlo and finite element mesh simulations of heat conduction, taking into account disordered geometry configurations with various φ and pore size, as well as laser-induced temperature distributions, respectively. At high φ, the decrease in k is additionally influenced by the disordering of the crystal structure, as evidenced by the near-surface sensitive TDTR and Rutherford backscattering spectroscopy measurements. Importantly, the k values measured by FDTR over larger depths inside np-Si were found to be anisotropic and lower than those detected by the near-surface sensitive TDTR and Raman thermal probes. This finding is supported by the cross-sectional scanning electron microscopy image indicating enhanced φ distribution over these micrometer-scale probed depths. Our study opens an avenue for nano-to-micrometer scale thermal depth profiling of porous semiconducting media with inhomogeneous porosity distributions applicable for efficient thermoelectric and thermal management.

Experimental study on the thermal conductivity of T-carbon

T-carbon, as one of new carbon allotropes that was first predicted and then successfully synthesized, has been attracting intensive research interest in recent years and has emerged potential applications in various areas. Here we use the frequency-domain thermoreflectance technique to measure for the first time the thermal conductivity (κ) of T-carbon, and report the power law behavior of κ(T) ∼ T−0.75 in T-carbon, with a value of 31.9 Wm−1K−1 at 300 K, which are nicely consistent with first-principles calculations (33.06 Wm−1K−1). Among all existing carbon crystals, we find that T-carbon has the lowest thermal conductivity, being nearly 50 times lower than that of cubic diamond, which is caused by the large scattering phase space and strong phonon anharmonicity of C–C bonds with sp3 hybridization in T-carbon. Our study reveals that T-carbon with particularly low thermal conductivity could have potential applications in energy converting devices, and the analyzed mechanism would deepen our understanding on the thermal transport and chemical bonding of carbon crystals.

Rapid subsurface analysis of frequency-domain thermoreflectance images with K-means clustering

K-means clustering analysis is applied to frequency-domain thermoreflectance (FDTR) hyperspectral image data to rapidly screen the spatial distribution of thermophysical properties at material interfaces. Performing FDTR while raster scanning a sample consisting of 8.6 μm of doped-silicon (Si) bonded to a doped-Si substrate identifies spatial variation in the subsurface bond quality. Routine thermal analysis at select pixels quantifies this variation in bond quality and allows assignment of bonded, partially bonded, and unbonded regions. Performing this same routine thermal analysis across the entire map, however, becomes too computationally demanding for rapid screening of bond quality. To address this, K-means clustering was used to reduce the dimensionality of the dataset from more than 20 000 pixel spectra to just K=3 component spectra. The three component spectra were then used to express every pixel in the image through a least-squares minimized linear combination providing continuous interpolation between the components across spatially varying features, e.g., bonded to unbonded transition regions. Fitting the component spectra to the thermal model, thermal properties for each K cluster are extracted and then distributed according to the weighting established by the regressed linear combination. Thermophysical property maps are then constructed and capture significant variation in bond quality over 25 μm length scales. The use of K-means clustering to achieve these thermal property maps results in a 74-fold speed improvement over explicit fitting of every pixel.

Interfacial Thermal Resistive Switching in (Pt,Cr)/SrTiO3 Devices.

The operation of oxide-based memristive devices relies on the fast accumulation and depletion of oxygen vacancies by an electric field close to the metal-oxide interface. Here, we show that the reversible change of the local concentration of oxygen vacancies at this interface also produces a change in the thermal boundary resistance (TBR), i.e., a thermal resistive switching effect. We used frequency domain thermoreflectance to monitor the interfacial metal-oxide TBR in (Pt,Cr)/SrTiO3 devices, showing a change of ≈20% under usual SET/RESET operation voltages, depending on the structure of the device. Time-dependent thermal relaxation experiments suggest ionic rearrangement along the whole area of the metal/oxide interface, apart from the ionic filament responsible for the electrical conductivity switching. The experiments presented in this work provide valuable knowledge about oxide ion dynamics in redox-based memristive devices.

Thermal Transport and Mechanical Stress Mapping of a Compression Bonded GaN/Diamond Interface for Vertical Power Devices.

Bonding diamond to the back side of gallium nitride (GaN) electronics has been shown to improve thermal management in lateral devices; however, engineering challenges remain with the bonding process and characterizing the bond quality for vertical device architectures. Here, integration of these two materials is achieved by room-temperature compression bonding centimeter-scale GaN and a diamond die via an intermetallic bonding layer of Ti/Au. Recent attempts at GaN/diamond bonding have utilized a modified surface activation bonding (SAB) method, which requires Ar fast atom bombardment immediately followed by bonding within the same tool under ultrahigh vacuum (UHV) conditions. The method presented here does not require a dedicated SAB tool yet still achieves bonding via a room-temperature metal-metal compression process. Imaging of the buried interface and the total bonding area is achieved via transmission electron microscopy (TEM) and confocal acoustic scanning microscopy (C-SAM), respectively. The thermal transport quality of the bond is extracted from spatially resolved frequency-domain thermoreflectance (FDTR) with the bonded areas boasting a thermal boundary conductance of >100 MW/m2·K. Additionally, Raman maps of GaN near the GaN-diamond interface reveal a low level of compressive stress, <80 MPa, in well-bonded regions. FDTR and Raman were coutilized to map these buried interfaces and revealed some poor thermally bonded areas bordered by high-stress regions, highlighting the importance of spatial sampling for a complete picture of bond quality. Overall, this work demonstrates a novel method for thermal management in vertical GaN devices that maintains low intrinsic stresses while boasting high thermal boundary conductances.

Inversion for Thermal Properties with Frequency Domain Thermoreflectance.

3D integration of multiple microelectronic devices improves size, weight, and power while increasing the number of interconnections between components. One integration method involves the use of metal bump bonds to connect devices and components on a common interposer platform. Significant variations in the coefficient of thermal expansion in such systems lead to stresses that can cause thermomechanical and electrical failures. More advanced characterization and failure analysis techniques are necessary to assess the bond quality between components. Frequency domain thermoreflectance (FDTR) is a nondestructive, noncontact testing method used to determine thermal properties in a sample by fitting the phase lag between an applied heat flux and the surface temperature response. The typical use of FDTR data involves fitting for thermal properties in geometries with a high degree of symmetry. In this work, finite element method simulations are performed using high performance computing codes to facilitate the modeling of samples with arbitrary geometric complexity. A gradient-based optimization technique is also presented to determine unknown thermal properties in a discretized domain. Using experimental FDTR data from a GaN-diamond sample, thermal conductivity is then determined in an unknown layer to provide a spatial map of bond quality at various points in the sample.

Thermal and Microstructural Characterization of GRCop-84/In718 Bi-metallic Structures Additively Manufactured by Directed Energy Deposition

As a nickel-based super alloy, Inconel 718 (In718) has gained attention in different industries due to its excellent mechanical behavior under elevated temperatures. Nevertheless, its low thermal conductivity limits its application in many fields, such as thermal energy conversion and heat dissipation. GRCop-84, in contrast, is a copper-based alloy with extremely high thermal conductivity. Making bi-metallic structures with GRCop-84 may expand the thermal-related applications of Inconel 718. In this study, we investigate the thermal properties of In718/GRCop-84 bi-metallic structures fabricated by the directed energy deposition (DED) technique with different process parameters of laser power and scanning velocity. The resulting microstructures were analyzed through scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS), while the frequency-domain thermoreflectance (FDTR) technique has been adopted to acquire the thermal properties. The melt pool thermal conductivities were 50 W/m K on single bead samples and 100 W/m K on single-layer pads, significantly lower than that of bulk GRCop-84. EDS analysis reveals large deviations from standard GRCop-84 compositions inside the melt pool.

Accelerated thermal property mapping of TRISO advanced nuclear fuel

TRistructural ISOtropic (TRISO) fuel is a leading-edge nuclear fuel form representing a departure from the more traditional nuclear fuel forms utilized in the reactor fleet of today. Rather than a monolithic fuel pellet of uranium dioxide, integral fuel forms containing TRISO fuel are composed of thousands of microencapsulated uranium-bearing fuel kernels and individually coated with multiple layers of pyrolytic carbon and silicon carbide. These multilayered ceramic coatings serve as an environmental barrier to ensure radioactive and chemically reactive fission products are contained within the reactor fuel elements, but also participate in the transfer of heat generated in the nuclear fuel to the coolant – the primary purpose of a nuclear reactor. Since traditional thermal property measurement techniques, such as laser flash analysis, would be unable to resolve the thermal properties of the individual TRISO coating layers, a simplified frequency-domain thermoreflectance technique has been developed to rapidly map the thermal properties of TRISO particles. Using this technique, the thermal properties of TRISO particles have been mapped from room temperature up to 1000 °C to examine the spatial variation and temperature-dependency of the thermal properties within each layer. Additionally, spatial-domain thermoreflectance was used to examine the anisotropy of the thermal properties for each layer at different locations within a single TRISO particle, and across multiple TRISO particles to assess the intra- and inter-particle uniformity of thermal properties, respectively. To elucidate the underlying causes for the measured variations in thermal properties, scanning electron microscopy and Raman spectroscopy were used to examine variations in microstructure and chemical bonding within the different coating layers. Results from this work are then compared with previous examinations of TRISO fuel particles and microstructurally driven mechanisms for the variations in the measured thermal properties of the different carbonaceous layers are discussed.

Using transducerless time-domain thermoreflectance technique to measure in- and cross-plane thermal conductivity of nanofilms

Time-domain thermoreflectance (TDTR) and frequency-domain thermoreflectance techniques have been widely used to measure thermal properties. However, the existence of the metal sensor brings some limitations to the experimental measurement, such as temperature limits, disability to measure low in-plane thermal conductivity, in situ measurement cannot be achieved, etc. This paper proposes a transducerless time-domain thermoreflectance method to measure in- and cross-plane thermal conductivity of nanofilms, in which the optical absorption depth and thermal conductivity tensor are considered to establish a new differential equation that can describe the heat conduction process in multilayer structures. This thermal model can also calculate the effects of spot ellipticity and spot offset distance. Then, the analytical solution and relative deviation of this new model and the surface heat flow boundary model used in conventional TDTR are compared by calculating the phase signals. In terms of experimental measurement, this model is successfully used to derive cross- and in-plane thermal conductivity of PdSi and IrNiTa amorphous alloy nanofilms without a metal sensor.

Reduced thermal resistance of amorphous Al2O3 thin films on β-Ga2O3 and amorphous SiO2 substrates via rapid thermal annealing

The impact of rapid thermal annealing (1000 °C for 1 min) on the thermal transport properties of amorphous alumina (a-Al2O3) thin films grown by atomic layer deposition on β−Ga2O3 and amorphous silica (a-SiO2) substrates is determined using frequency-domain thermoreflectance measurements. The annealing more than doubles the a-Al2O3 thermal conductivity for both substrates (1.54 ± 0.13 to 3.14 ± 0.27 W m−1 K−1 for β−Ga2O3 and 1.60 ± 0.14 to 3.87 ± 0.33 W m−1 K−1 for a-SiO2) while keeping the film amorphous. The thermal conductivity increase is attributed to partial recrystallization and off-gassing of embedded impurities. Annealing halves the thermal boundary resistance of the a-Al2O3/a-SiO2 interface (10.5 ± 1.0 to 4.47 ± 0.42 m2 K GW−1), which is attributed to compositional mixing and structural reorganization that are enabled by the elastic matching of these two materials. The thermal boundary resistance of the a-Al2O3/β−Ga2O3 interface is not affected by annealing due to the elastic mismatch. Reducing the thermal resistance of a-Al2O3 dielectric films and adjacent interfaces by annealing will promote lateral heat spreading adjacent to hot spots and improve device longevity.

Microscale Imaging of Thermal Conductivity Suppression at Grain Boundaries.

Grain-boundary engineering is an effective strategy to tune the thermal conductivity of materials, leading to improved performance in thermoelectric, thermal-barrier coatings and thermal management applications. Despite the central importance to thermal transport, a clear understanding of how grain boundaries modulate the microscale heat flow is missing, owing to the scarcity of local investigations. Here, thermal imaging of individual grain boundaries is demonstrated in thermoelectric SnTe via spatially resolved frequency-domain thermoreflectance. Measurements with microscale resolution reveal local suppressions in thermal conductivity at grain boundaries. Also, the grain-boundary thermal resistance - extracted employing a Gibbs excess approach - is found correlating with the grain-boundary misorientation angle. Extracting thermal properties, including thermal boundary resistances, from microscale imaging can provide comprehensive understanding of how microstructure affects heat transport, crucially impacting the materials design of high-performance thermal-management and energy-conversion devices. This article is protected by copyright. All rights reserved.

Engineering Heat Transport Across Epitaxial Lattice-Mismatched van der Waals Heterointerfaces.

Artificially engineered 2D materials offer unique physical properties for thermal management, surpassing naturally occurring materials. Here, using van der Waals epitaxy, we demonstrate the ability to engineer extremely insulating thermal metamaterials based on atomically thin lattice-mismatched Bi2Se3/MoSe2 superlattices and graphene/PdSe2 heterostructures with exceptional thermal resistances (70-202 m2 K/GW) and ultralow cross-plane thermal conductivities (0.012-0.07 W/mK) at room temperature, comparable to those of amorphous materials. Experimental data obtained using frequency-domain thermoreflectance and low-frequency Raman spectroscopy, supported by tight-binding phonon calculations, reveal the impact of lattice mismatch, phonon-interface scattering, size effects, temperature, and interface thermal resistance on cross-plane heat dissipation, uncovering different thermal transport regimes and the dominant role of long-wavelength phonons. Our findings provide essential insights into emerging synthesis and thermal characterization methods and valuable guidance for the development of large-area heteroepitaxial van der Waals films of dissimilar materials with tailored thermal transport characteristics.