Underlayer Research Articles

Nitrogen vacancies in GaN templates and their critical role on the luminescence efficiency of blue quantum wells.

In InGaN-based LEDs, an InGaN layer underlying active region has been widely used to improve the luminescence efficiency of the quantum wells (QWs). It has been reported recently that the role of InGaN underlayer (UL) is to block the diffusion of point defects or surface defects in n-GaN into QWs. The type and the source of the point defects need further investigations. In this paper, using temperature-dependent photoluminescence (PL) measurements, we observe emission peak related to nitrogen vacancies (VN) in n-GaN. In combination with secondary ion mass spectroscopy (SIMS) measurement and theoretical calculation, it is found that VN concentration in n-GaN is as high as about 3 × 1018 cm-3 in n-GaN grown with low growth V/III ratio and can be suppressed to about 1.5 × 1016 cm-3 by increasing growth V/III ratio. Luminescence efficiency of QWs grown on n-GaN under high V/III ratio is greatly improved. These results indicate high density of nitrogen vacancies are formed in n-GaN layer grown under low V/III ratio and diffuse into quantum wells during epitaxial growth and reduce the luminescence efficiency of the QWs.

Defect incorporation in In-containing layers and quantum wells: experimental analysis via deep level profiling and optical spectroscopy

Recent studies demonstrated that the performance of InGaN/GaN quantum well (QW) light emitting diodes (LEDs) can be significantly improved through the insertion of an InGaN underlayer (UL). The current working hypothesis is that the presence of the UL reduces the density of non-radiative recombination centers (NRCs) in the QW itself: during the growth of the UL, surface defects are effectively buried in the UL, without propagating towards the QW region. Despite the importance of this hypothesis, the concentration profile of defects in the quantum wells of LEDs with and without the UL was never investigated in detail. This paper uses combined capacitance-voltage and steady-state photocapacitance measurements to experimentally identify the defects acting as NRCs and to extract a depth-profile of the traps, thus proving the incorporation upon indium-reaction. Specifically: (i) we demonstrate that LEDs without UL have a high density (9.2 × 1015 cm−3) of defects, compared to samples with UL (0.8 × 1015 cm−3); (ii) defects are located near midgap (E C-1.8 eV, corresponding to E i-E T ∼ 0.3 eV), thus acting as efficient NRCs; (iii) crucially, the density of defects has a peak within the QWs, indicating that traps are segregated at the first grown InGaN layers; (iv) we propose a model to calculate trap distribution in the QW, and we demonstrate a good correspondence with experimental data. These results provide unambiguous demonstration of the role of UL in limiting the propagation of defects towards the QWs, and the first experimental characterization of the properties of the related traps.

Deep traps in InGaN/GaN single quantum well structures grown with and without InGaN underlayers

The electrical properties and deep trap spectra were compared for near-UV GaN/InGaN quantum well (QW) structures grown on free-standing GaN substrates. The structures differed by the presence or absence of a thin (110 nm) InGaN layer inserted between the high temperature GaN buffer and the QW region. Capacitance-voltage profiling with monochromatic illumination showed that in the InGaN underlayer (UL), the density of deep traps with optical threshold near 1.5 eV was much higher than in the QW and higher than for structures without InGaN. Irradiation with 5 MeV electrons strongly increased the concentration of these 1.5 eV traps in the QWs, with the increase more pronounced for samples without InGaN ULs. The observations are interpreted using the earlier proposed model explaining the impact of In-containing underlayers by segregation of native defects formed during growth of GaN near the surface and trapping of these surface defects by In atoms of the InGaN UL, thus preventing them from infiltrating the InGaN QW region. Deep level transient spectroscopy (DLTS) also revealed major differences in deep trap spectra in the QWs and underlying layers of the samples with and without InGaN ULs. Specifically, the introduction of the InGaN UL stimulates changing the dominant type of deep traps. Irradiation increases the densities of these traps, with the increase being more pronounced for samples without the InGaN UL. It is argued that light emitting diodes (LEDs) with InGaN UL should demonstrate a higher radiation tolerance than LEDs without InGaN UL.

Role of Underlayer for Efficient Core-Shell InGaN QWs Grown on m-plane GaN Wire Sidewalls.

Different types of buffer layers such as InGaN underlayer (UL) and InGaN/GaN superlattices are now well-known to significantly improve the efficiency of c-plane InGaN/GaN-based light-emitting diodes (LEDs). The present work investigates the role of two different kinds of pregrowth layers (low In-content InGaN UL and GaN UL namely "GaN spacer") on the emission of the core-shell m-plane InGaN/GaN single quantum well (QW) grown around Si-doped c̅-GaN microwires obtained by silane-assisted metal organic vapor phase epitaxy. According to photo- and cathodoluminescence measurements performed at room temperature, an improved efficiency of light emission at 435 nm with internal quantum efficiency >15% has been achieved by adding a GaN spacer prior to the growth of QW. As revealed by scanning transmission electron microscopy, an ultrathin residual layer containing Si located at the wire sidewall surfaces favors the formation of high density of extended defects nucleated at the first InGaN QW. This contaminated residual incorporation is buried by the growth of the GaN spacer and avoids the structural defect formation, therefore explaining the improved optical efficiency. No further improvement is observed by adding the InGaN UL to the structure, which is confirmed by comparable values of the effective carrier lifetime estimated from time-resolved experiments. Contrary to the case of planar c-plane QW where the improved efficiency is attributed to a strong decrease of point defects, the addition of an InGaN UL seems to have no influence in the case of radial m-plane QW.

Effects of InAlN underlayer on deep traps detected in near-UV InGaN/GaN single quantum well light-emitting diodes

Two types of near-UV light-emitting diodes (LEDs) with an InGaN/GaN single quantum well (QW) differing only in the presence or absence of an underlayer (UL) consisting of an InAlN/GaN superlattice (SL) were examined. The InAlN-based ULs were previously shown to dramatically improve internal quantum efficiency of near-UV LEDs, via a decrease in the density of deep traps responsible for nonradiative recombination in the QW region. The main differences between samples with and without UL were (a) a higher compensation of Mg acceptors in the p-GaN:Mg contact layer of the sample without UL, which correlates with the presence of traps with an activation energy of 0.06 eV in the QW region, (b) the presence of deep electron traps with levels 0.6 eV below the conduction band edge (Ec) (ET1) and at Ec 0.77 eV (ET2) in the n-GaN spacer underneath the QW, and the presence of hole traps (HT1) in the QW, 0.73 eV above the valence band edge in the sample without UL (no traps could be detected in the sample with UL), and (c) a high density of deep traps with optical ionization energy close to 1.5 eV for the LEDs without UL. Irradiation with 5 MeV electrons led to a strong decrease in the electroluminescence (EL) intensity in the LEDs without UL, while for the samples with UL, such irradiation had little effect on the EL signal at high driving current, although the level of driving currents necessary to have a measurable EL signal increased by about an order of magnitude. This is despite the 5 times higher starting EL signal of the sample with UL. Irradiation also led to the appearance in the LEDs with UL of the ET1 and HT1 deep traps, but with concentration much lower than without the UL, and to a considerable increase in the Mg compensation ratio.

InGaN quantum wells with improved photoluminescence properties through strain-controlled modification of the InGaN underlayer

The effect of internal strain on the luminescence properties of an InGaN single quantum well (SQW) was investigated as a function of modification via an underlayer (UL). Single In0.25Ga0.75N QWs (λ = 520 nm) 3 nm thick were grown on various ULs on a sapphire substrate, where the two UL types included (1) a buffer layer onto which an InGaN layer with a very small amount of In was inserted and (2) a buffer layer grown using different carrier gases. The SQWs were then analyzed by temperature-dependent time-resolved photoluminescence, scanning electron microscopy and cathodoluminescence. The experimental results show that the density of non-radiative recombination centers and the level of potential fluctuation in the SQWs decrease with insertion of an InxGa1−xN UL possessing a quite low but sufficient indium content (x = 0.007). The density of non-radiative recombination centers in the SQW on the H2 carrier-grown UL, however, is large.

InAlN underlayer for near ultraviolet InGaN based light emitting diodes

We report on InAlN underlayer (UL) to improve the efficiency of near ultraviolet (NUV) light emitting diodes (LEDs). While InGaN UL is commonly used in high-efficiency blue LEDs it may absorb light for shorter wavelengths. InAlN lattice-matched to GaN exhibits a bandgap of 4.6 eV. This allows alleviating absorption issues in NUV LEDs. We demonstrate that the internal quantum efficiency of 405 nm single InGaN/GaN quantum well LEDs with InAlN UL is ∼70% compared to less than 10% for LEDs without UL. Excellent I–V characteristics are achieved thanks to polarization charge screening with high doping level at the InAlN/GaN interface.

Underlayer dependence of electric field effect on magnetic anisotropy and its volatility in CoFeB/MgO structures

We report the dependence of voltage-controlled magnetic anisotropy (VCMA) effect and its volatility on an underlayer (UL) in CoFeB/MgO structures. For a sample with Ta or Pt UL, the VCMA effect occurs when the applied gate voltage (Vg) exceeds a critical value, and it persists even after removing Vg. This is in contrast to the volatile VCMA effect and its linear dependence on Vg in a sample with W UL. Furthermore, we demonstrate that the volatility of the VCMA effect can be modified by introducing a Ta/W bilayer, enabling arbitrary control of the magnetic properties via VCMA effect.

GaN surface as the source of non-radiative defects in InGaN/GaN quantum wells

Blue light-emitting diodes based on III-nitride semiconductors are nowadays widely used for solid-state lighting. They exhibit impressive figures of merit like an internal quantum efficiency close to 100%. This value is intriguing when considering the high dislocation density running throughout the InGaN/GaN quantum well (QW) active region. This striking feature is currently ascribed to carrier localization occurring in the InGaN alloy, which hinders their diffusion toward dislocations. However, it was recently reported that another source of defects, disconnected from dislocations, dramatically decreases the radiative efficiency of InGaN/GaN QWs. Those defects, present at the surface, are usually trapped in an InGaN underlayer (UL), which is grown before the QW active region. To get insight into the trapping mechanism, we varied the UL thickness, In content, and materials system (InGaN or InAlN) and studied the photoluminescence decay time at 300 K of a single InGaN/GaN QW. Our data demonstrate that defects are incorporated proportionally to the indium content in the UL. In addition, we show that those defects are created during the high-temperature growth of GaN and that they segregate at the surface even at low-temperature. Eventually, we propose an intrinsic origin for these surface defects.

Burying non-radiative defects in InGaN underlayer to increase InGaN/GaN quantum well efficiency

The insertion of an InGaN underlayer (UL) is known to strongly improve the performance of InGaN/GaN quantum well (QW) based blue light emitting diodes (LEDs). However, the actual physical mechanism responsible for it is still unclear. We thus conduct a systematic study and investigate different hypotheses. To this aim, InGaN/GaN single (S) QWs are grown on sapphire and GaN free-standing substrates with or without InGaN UL. This allows us to conclude that (i) improvement of LED performance is due to a higher internal quantum efficiency of the InGaN/GaN SQW and (ii) reduction of structural defects is not at play. Furthermore, we show that neither the surface morphology nor the strain of the top GaN layer before the growth of the QW is affected by the InGaN UL. Finally, we find that the beneficial effect of the InGaN UL is still present after 100 nm of GaN. This result combined with band structure modelling rules out the hypothesis of higher QW oscillator strength induced by a reduction of the internal electric field due to band bending. In conclusion, we demonstrate that the increase in InGaN/GaN QW efficiency is the consequence of a reduction of non-radiative recombination centers in the QW itself, independent of the dislocation density.

Effects of ultraviolet and vacuum ultraviolet synchrotron radiation on organic underlayers to modulate line-edge roughness of fine-pitch poly-silicon patterns

Deformation of the pattern or the increase in line roughness during plasma etching becomes more significant with the shrink of complementary metal–oxide–semiconductor patterns. For aggressively scaled patternings, an organic underlayer (UL) is often used under the photoresist and a thin layer of a Si-containing hardmask. In this work, the effect of ultraviolet/vacuum ultraviolet (VUV) photons on UL parameters such as wavelength, photon dose, and process order was investigated using synchrotron radiation. First, the index of refraction and extinction coefficients of mask materials such as e-beam resist [hydrogen silsesquioxane (HSQ)] and organic UL (NFC-1400; NFC) were measured by utilizing the Kramers–Kronig relations and/or ellipsometry measurements depending on the wavelength involved. Second, VUV photons at specific wavelengths, corresponding to absorption maxima of HSQ and NFC at 54 nm (HSQ), 62 nm (HSQ and NFC), 88 nm (HSQ), 112 nm (NFC), 138 nm (HSQ), 155 nm (NFC), 194 nm (NFC), and 238 nm (NFC), were exposed before or/and after etching of NFC. The authors continued to etch into poly-Si, and the resulting line-edge roughness (LER) was measured. The improvement of the LER was seen at the wavelengths corresponding to the absorption maxima of NFC, and the degree of LER improvement was better at the higher photon dose up to 3 × 1017 photons/cm2. The LER reduced from 6.7 to 4.2 nm and to 3.6 nm when the VUV photons at wavelengths of 62 and 155 nm, respectively, were used for exposure. In contrast, pattern degradation was observed at the wavelengths corresponding to the absorption maxima of HSQ. These findings indicate that optimizing VUV radiation corresponding to the UL materials greatly influences the LER.

Enhanced tunnel magnetoresistance and electric-field effect in CoFeB/MgO/CoFeB perpendicular tunnel junctions with W underlayer

We investigated the dependence of tunnel magnetoresistance (TMR) and its electric-field effect in CoFeB/MgO/CoFeB magnetic tunnel junctions (MTJ) on different underlayer (UL) materials. We observed enhancements in the TMR ratio and its temperature dependence as well as electric-field effect in MTJs with W UL, as compared to those in MTJs with a conventional Ta UL. This is attributed to better thermal stability of perpendicular magnetic anisotropy (PMA) in W/CoFeB/MgO, which sustains up to 380 °C, compared to that of Ta/CoFeB/MgO which starts to degrade at 270 °C. This demonstrates that the PMA in a CoFeB/MgO structure and its electric-field dependence can be enhanced by the careful selection of underlayer, opening the way for the realization of electric-field effect-driven spintronic devices.

Surfactant and TiO2 underlayer derived porous hematite nanoball array photoanode for enhanced photoelectrochemical water oxidation

Controlling the morphology of semiconductors at the nanoscale level is the key for efficient photoelectrochemical (PEC) water splitting systems. Herein, we report for the first time the fabrication of porous hematite nanoball array film on conducting FTO via a facile pulse reverse electrodeposition method using cetyltrimethylammonium bromide (CTAB) surfactant and a TiO2 underlayer (UL) on FTO. A prolonged low-temperature-annealing treatment is employed to convert iron into hematite (α-Fe2O3) and to remove the surfactant molecules gradually. Annihilation of surfactant molecules led to the creation of pores during crystallization of hematite nanoballs, thereby providing low-resistant diffusion pathways for the migration and incorporation of cations (Ti4+ from UL and Sn4+ from FTO) in hematite. The hematite photoanode with porous nanoball array exhibited significantly higher PEC performance than the flat hematite due to sixfold enrichment in the donor density, improved charge-transfer properties, and higher light absorption. The enhancement in photocurrent and water oxidation performance of porous hematite photoanode is also feasible when coupled with well-known Co and CoPi catalysts. Thus, our new approach allowed the simple fabrication of hematite films with nanoporous architecture for enabling high photon harvesting and maximized interfacial charge transfer to facilitate water oxidation reaction.

A Synergistic Effect of Surfactant and ZrO2 Underlayer on Photocurrent Enhancement and Cathodic Shift of Nanoporous Fe2O3 Photoanode.

Augmenting the donor density and nanostructure engineering are the crucial points to improve solar water oxidation performance of hematite (α-Fe2O3). This work addresses the sluggish water oxidation reaction associated with hematite photoanode by tweaking its internal porosity. The porous hematite photoanodes are fabricated by a novel synthetic strategy via pulse reverse electrodeposition (PRED) method that involves incorporation of a cationic CTAB surfactant in a sulfate electrolyte and spin-coated ZrO2 underlayer (UL) on FTO. CTAB is found to be beneficial in promoting the film growth rate during PRED. Incorporation of Zr4+ ions from ZrO2 UL and Sn4+ ions from FTO into the Fe2O3 lattice via solid-state diffusion reaction during pertinent annihilation of surfactant molecules at 800 °C produced internally porous hematite films with improved carrier concentration. The porous hematite demonstrated a sustained photocurrent enhancement and a significant cathodic shift of 130 mV relative to the planar hematite under standard illumination conditions (AM 1.5G) in 1 M NaOH electrolyte. The absorption, electrochemical impedance spectroscopy and Mott-Schottky analyses revealed that the ZrO2 UL and CTAB not only increased the carrier density and light harvesting but also accelerated the surface oxidation reaction kinetics, synergistically boosting the performance of internally porous hematite photoanodes.

Improved performance of AlGaN-based deep ultraviolet light-emitting diodes with n-AlGaN underlayers

We demonstrate notable performance improvement of 270 nm deep ultraviolet light-emitting diodes (DUV-LEDs) by inserting an n-AlGaN underlayer (UL), which was directly beneath an AlGaN multiple quantum well (MQW) active region. This DUV-LED exhibited significantly improved forward and reverse bias current-voltage characteristics, and spectral properties. As a result, the turn-on voltage was decreased from 7 to 4.6 V by introducing the n-AlGaN UL, and the maximum light output power and external quantum efficiency of DUV-LEDs with the n-AlGaN UL, obtained via on-wafer measurement, were increased by factors of 3.6 and 2.2, respectively. Further enhancements can be realized by using high-quality AlN/sapphire templates together with the n-AlGaN UL. These improvements were considered to be attributed to the introduction of the n-AlGaN UL which improved electron injection and reduced the quantum confined stark effect in the AlGaN MQWs.

Defect-reduction mechanism for improving radiative efficiency in InGaN/GaN light-emitting diodes using InGaN underlayers

The influence of a dilute InxGa1-xN (x ∼ 0.03) underlayer (UL) grown below a single In0.16Ga0.84N quantum well (SQW), within a light-emitting diode (LED), on the radiative efficiency and deep level defect properties was studied using differential carrier lifetime (DCL) measurements and deep level optical spectroscopy (DLOS). DCL measurements found that inclusion of the UL significantly improved LED radiative efficiency. At low current densities, the non-radiative recombination rate of the LED with an UL was found to be 3.9 times lower than the LED without an UL, while the radiative recombination rates were nearly identical. This suggests that the improved radiative efficiency resulted from reduced non-radiative defect concentration within the SQW. DLOS measurement found the same type of defects in the InGaN SQWs with and without ULs. However, lighted capacitance-voltage measurements of the LEDs revealed a 3.4 times reduction in a SQW-related near-mid-gap defect state for the LED with an UL. Quantitative agreement in the reduction of both the non-radiative recombination rate (3.9×) and deep level density (3.4×) upon insertion of an UL corroborates deep level defect reduction as the mechanism for improved LED efficiency.

(Invited) The Novel Spin-on Hard Mask and Ultra Thin UL Material for EUVL

For below Hp22nm generation, Hard-mask strategy is one of the key issues to achieve the good balance for Lithography and Etching performance. The thickness of resist should be thicker enough to obtain the etching margin for the substrate etching. However, the thickness of photo resist (PR) needs to be thinner to obtain the good pattern collapse margin and resolution. In order to solve this tread-off, the spin-on hard mask (HM) technology can be applied. On the other hand, the ultra thin organic Underlayer (UL) being combined with the CVD-HM film stack is also one of the processes for EUV lithography. In order to avoid the film loss of resist during UL open, the thickness of UL must be thinner and the etch rate need to be faster. We studied the effect of UL design and thickness for the EUV lithography performance. For EUV lithography, the electron generation effect from UL is one of the key factors to improve the patterning performance of resist. In this paper, we studied the suitable functional group for the Silicon containing HM(Si-HM) for multilayer process and Org.-UL, which has high potential to generate 2nd electron and enhance the resist performance, and discuss the material design and performance.

Application of soft X-ray reflectometry for analysis of underlayer influence on structure of atomic-layer deposited SrTixOy films

We explored the possibility to quantify the atomic in-depth distributions by using the energy-dependent soft X-ray reflectivity (SXRR) measurements, in particular, the possibility to obtain the profiles of low-Z elements [C, N, O, Si] in heterostructures containing high concentration of higher-Z atoms [Ti, Sr, Hf]. We have shown that the SXRR technique allows one not only to quantify the atomic composition of the Sr-rich SrTixOy insulators grown on (100)Si by the Atomic Layer Deposition method but also to obtain atomic profiles across a few-nm thick underlayer (UL) inserted between SrTixOy film and the Si substrate. The accuracy of atomic concentrations and densities estimated is already sufficient to trace even small variations in composition of the SrTixOy grown by ALD on the chemically different underlayers and most it is important the composition and extension of an interfaces.

Development of Under Layer Material for EUV Lithography

For the next generation lithography (NGL), several technologies have been proposed to achieve the 22nm-node devices and beyond. Extreme ultraviolet (EUV) lithography is one of the candidates for the next generation lithography. For lithography processes, the Line width roughness (LWR) and the pattern collapse of resist are the most critical issues for NGL, because of the small target critical dimension (CD) size and high aspect ratio. In this study, we design the new concept of EUV Under layer (UL) material to meet these requirements and study the impact of polymer design for pattern collapse behavior, pattern profile and LWR control by using EUV exposure tool.

Boosting Green GaInN/GaN Light-Emitting Diode Performance by a GaInN Underlying Layer

The light output of 530 nm green GalnN/GaN light-emitting diodes on sapphire has been nearly doubled by the insertion of a 130-nm GalnN underlayer (UL) between the n-GaN electron injection layer and the quantum-well (QW) active region. Under variation of the alloy composition, best results were obtained for an x = 6.3% Ga <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">1-x</sub> In <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">x</sub> N UL. By low-temperature depth-resolved cathodoluminescence spectroscopy, an interplay of the impurity-related donor-acceptor pair recombination, the UL, and the QW emission has been observed. We propose that the resonance and level alignments between the defect and UL levels reroute excitation toward radiative recombination in the QWs.