Hole Trapping Research Articles

Depth profiles of hole traps in the tail region of Al ion implantation into p-type 4H-SiC

Abstract Hole traps generated in the tail region of Al ion implantation in p-type 4H-SiC were characterized by deep level transient spectroscopy measurements. Hole traps energetically located at Ev + 0.51 eV, Ev + 0.72 eV, Ev + 0.77 eV, and Ev + 1.40 eV (Ev : energy of the valence band top) were detected. The hole trap densities were roughly 7–40 times smaller than the implanted Al atom density in the tail region, and the densities of the observed traps exponentially decreased with the decay lengths of 84–150 nm.

Liquid nitrogen temperature to 700 K Bi3+ thermoluminescence: Toward wide-temperature-range light dosimeters for versatile anti-counterfeiting, information storage, and x-ray imaging

Discovering light dosimeters that can function effectively from liquid nitrogen temperature to 700 K presents significant challenges. Such dosimeters facilitate a range of cutting-edge applications, including anti-counterfeiting measures at low temperature for cryo-preservation. To facilitate such discovery, stacked vacuum referred binding energy diagrams for the LiYGeO4 cluster of crystals have been first constructed. They offer a robust method for controlling both electron and hole trapping depth in the LiYGeO4 cluster of crystals. Wide temperature shifting of Bi2+ and Eu2+ thermoluminescence (TL) glow bands emerges from 200 to 500 K for LiYxLu1-xGeO4:0.01Bi3+ and LiYxLu1-xGeO4:0.01Bi3+, 0.001Eu3+, by changing x, facilitating conduction band tailoring. Wide temperature shifting of Bi4+ TL glow bands emerges from 300 to 700 K for LiYGezSi1-zO4:0.01Bi3+, by tuning z, facilitating valence band tailoring. TL glow band peaks near 135, 185, 232, and 311 K emerge in LiyNa1-yYGeO4: 0.001Bi3+. Particularly, the discovered Bi3+ or/and lanthanide modified LiYGeO4 cluster of crystals exhibit superior charge carrier storage capacity and minimal TL fading properties. For instance, the ratio of TL intensity of the optimized LiYGe0.75Si0.25O4:0.001Bi3+ to that of industrial BaFBr(I):Eu2+ is as high as ∼4. Interestingly, imaging of intense optically driven Bi3+ ultraviolet-A (UVA) luminescence has been validated in 254 nm energized LiY0.25Lu0.75GeO4:0.01Bi3+ with a 100 lux white LED illumination. Together with ZnS:Mn2+, LiTaO3:Bi3+, Sm3+, and Cs2ZrCl6:Sb3+ perovskites, the realization of wide range liquid nitrogen temperature to 700 K Bi3+ thermoluminescence in Bi3+ or/and lanthanide modified LiYGeO4 cluster of crystals with superior charge carrier storage capacity offers promising use for versatile anti-counterfeiting, information storage, and delayed x-ray imaging purposes.

Adopting Buffer Layer for Improving Signal‐to‐Noise Ratio of Broadband Photomultiplication Type Organic Photodetectors

AbstractThe photomultiplication type organic photodetectors (PM‐OPDs) are prepared with structure of ITO/PNDIT‐F3N/F8BT/Y6‐1O:P3HT (100:3, wt/wt)/Al, containing hole traps formed with P3HT surrounded by Y6‐1O in active layers. The PM‐OPDs exhibit external quantum efficiency (EQE)>100% in the spectral response range from 310 to 910 nm, resulting from electron tunneling injection assisted by trapped hole near ITO electrode. The incorporation of F8BT buffer layers can induce the markedly decreased dark current density (JD) due to the large electron injection barrier. The light current density (JL) of PM‐OPDs exhibits slightly decreased by inserting F8BT buffer layers due to the enhanced electron tunneling injection assisted by the more trapped holes near ITO electrode. The signal‐to‐noise ratio (SNR) of PM‐OPDs achieves over 40‐fold increment by inserting appropriate thickness of F8BT buffer layers, resulting from the markedly decreased JD and reasonably high JL. The optimal PM‐OPDs exhibit excellent photodetection capability with EQE of 4200% at 360 nm and 6600% at 850 nm, associated with the specific detectivity of 3.9 × 1011 Jones at 360 nm and 9.7 × 1011 Jones at 850 nm.

Charge Carrier Dynamics at the Perovskite Interface with Self-Assembled Monolayers.

Self-assembled monolayers (SAMs) deposited on the hole-collecting electrodes of p-i-n perovskite solar cells effectively replace bulky hole transporting layers. However, the mechanism by which monolayers control the electronic processes and how they depend on the properties of the monolayer molecules remain poorly understood. In this study, we developed a simplified perovskite solar cell imitator with blocked electron extraction to investigate the photocurrent dynamics between the perovskite and the hole-collecting ITO electrode. We investigated the photoluminescence and photovoltage dynamics under short laser pulse excitation and addressed the influence of bulky and monomolecular hole transport layers. Our findings reveal that the photovoltage dynamics is significantly affected by the properties of the transport and perovskite layers, which in turn depend on the methods of sample preparation and exploration. Photocurrent dynamics is determined by several processes, including charge carrier displacement in the local electric field, hole transport to ITO, trapping of holes in interface trap states, and electron-hole recombination at the interface. We propose a model that takes into account molecular dipole moments and their ionization potentials to partially explain the different influences of different monolayers on the hole extraction and interfacial recombination rates. Additionally, the photovoltage dynamics also strongly depends on the illumination of the sample and shows memory effects that persist over minutes and hours and are attributed to the redistribution of ions.

Quantitative Spectroscopic Analysis of Surface-Reaching Photoexcited Holes in g-C3N4/TiO2 Z-Scheme Heterojunctions.

The Z-scheme heterojunction has been demonstrated to be effective in tuning the photocatalytic performance of photocatalysts. However, there is still a lack of quantitative and in-depth research on how the Z-scheme heterojunction affects the concentration of surface-reaching photoexcited charges. Here, by combining time-resolved spectroscopies and kinetic analysis, the concentration of surface-reaching photoholes (Ch+(surf)) within g-C3N4/TiO2 Z-scheme heterojunctions was quantitatively analyzed for the first time. Quantitative measurements reveal that Ch+(surf) of the prepared Z-scheme photocatalysts is highly dependent on the g-C3N4 content and the induced Z-scheme heterojunctions at the g-C3N4/TiO2 interface. Encouragingly, we found that a properly engineered Z-scheme heterojunction with close coupling of g-C3N4 and TiO2 can significantly increase the Ch+(surf), leading to nearly a 1.7-fold increase compared with pristine TiO2 samples. Furthermore, a distinct hole trap state-mediated Z-scheme charge transfer mechanism was uncovered in which the intrinsic interface defects at the g-C3N4/TiO2 junction act as hole traps, accelerating interface electron-hole recombination, thereby boosting spatial charge separation and ultimately enriching the Ch+(surf). This work provides insights into understanding and controlling electron pathways and Ch+(surf) in Z-scheme photocatalysis, with implications for the screening of different types of direct Z-scheme photocatalysts.

Synthesis of β-Ga2O3:Mg Thin Films by Electron Beam Evaporation and Postannealing

Doping divalent metal cations into Ga2O3 films plays a key role in adjusting the conductive behavior of the film. N-type high-resistivity β-Ga2O3:Mg films were prepared using electron beam evaporation and subsequent postannealing processing. Various characterization methods (X-ray diffraction, X-ray photoelectron spectroscopy, photoluminescence, etc.) revealed that the Mg content plays an important role in affecting the film quality. Specifically, when the Mg content in the film is 3.6%, the S2 film’s resistivity, carrier content, and carrier mobility are 59655.5 Ω·cm, 1.95 × 1014 cm3/C, and 0.53682 cm2/Vs. Also, the film exhibits a smoother surface, more refined grains, and higher self-trapped exciton emission efficiency. The Mg cation mainly substitutes the Ga+ cation at a tetrahedral site, acting as a trap for self-trapped holes.

Suppression of the hole trap for high-quality amino-phosphine based InP quantum dots

InP quantum dots (QDs) have emerged as promising nanomaterials in various fields due to their exceptional optical properties. However, its wide emission linewidth limits further application. In this study, we synthesized high-quality InP/ZnSe/ZnS QDs by suppressing hole defects. The unreacted In precursors during nucleation easily enter ZnSe in the subsequent shelling process, forming a hole trapping center that adversely affects the photo-excitons radiative recombination. Our results demonstrate that the presence of In ions in ZnSe shell enhances exciton-phonon coupling, broadens the fluorescence emission spectrum, and weakens exciton binding energy. The optimized InP QDs exhibit a line width of 44 nm and 90% PLQY at 630 nm. Furthermore, our investigation into the interaction between shell hole defects and core exciton function provides valuable insights for designing and preparing another high-performance core-shell heterojunction QDs.

Response-Enhanced GeSn Photodetectors Realized by Photon Trapping Holes Array

Response-Enhanced GeSn Photodetectors Realized by Photon Trapping Holes Array

Formation of a combined electron-hole emission state in the LiRbSO4 – Eu phosphor

In the irradiated phosphor 4 LiRbSO Eu , the mechanisms of formation of the induced or combined electron-emitting state at 3.1-2.94 eV were studied using optical and thermal activation spectroscopy methods. It has been shown experimentally that the combined electron-emitting state of the phosphor is formed from the electron states of impurity and intrinsic electron and hole trapping centers of 24Eu SO   and 34 4 SO SO . Electron and hole trapping centers are created by irradiating the phosphor with photons exceeding the width of the forbidden band of the matrix, where free electrons are created in the conduction band and a hole in the valence band. The trapping center is formed by the capture of free electrons by impurities and anionic complexes according to the reaction 3 2 Eu e Eu      ,2 34 4 SO e SO    . In one process with electron centers, holes in the form of 24SO are localized. Thus, impurity and intrinsic 2 4Eu SO   and 34 4 SO SO  electron-hole trapping centers are formed. Similarly, trapping centers are formed as a result of charge transfer from the excited anion of the 24SO complex to the 3Eu  impurities and to the neighboring 2 4 SO anions according to the reaction ( 2 3 O Eu   ) and ( 2 24O SO  ), and localized holes are also formed in one act along with it. Combined electron-emitting states consisting of impurity and intrinsic electron states are excited by photons with energies of ~4.0 eV and ~4.5 eV.

Low temperature recombination luminescence of Mg3Y2Ge3O12:Tb3+

A study was conducted to examine the recombination processes in persistent phosphor Mg3Y2Ge3O12:Tb3+ garnet at low temperatures. Photoluminescence (PL), recombination luminescence (RL), electron paramagnetic resonance (EPR), and EPR detected by PL or RL were measured.In samples with low Tb3+ concentration, a broad PL and RL band around 400–450 nm and characteristic Tb3+ lines were observed. However, in samples with high Tb3+ concentration, only Tb3+ lines were present. Both the broad-band and the line components exhibit long-lasting tunneling luminescence with hyperbolic decay. After 263 nm UV irradiation signals of intrinsic electron (F-type) and hole (V-type) trapping centres were observed in the EPR spectra. Such signals were also observed in RL-detected EPR spectra, indicating that the broad RL band at low Tb3+ concentrations originates from tunneling recombination between these intrinsic traps. At high Tb3+ concentrations, the RL-EPR spectrum was not observed, suggesting that intrinsic electron and Tb-related hole trapping centres probably participate in the tunneling recombination.

Synergy of Ag and Interfacial Oxygen Vacancies on TiO2 for Highly Efficient Photocatalytic Production of H2O2.

Photocatalytic H2O2 production stands as a promising sustainable technology for chemical synthesis. However, rapid charge recombination and limited oxygen adsorption by photocatalysts often limit its efficiency. Herein, we demonstrate that the synergy of Ag and interfacial oxygen vacancies on TiO2 could overcome these challenges. The optimized Ag/TiO2-50 photocatalyst achieved an impressive H2O2 production rate of 12.9 mmol h-1 g-1 and maintained a steady-state concentration of 12.8 mM, significantly outperforming most TiO2-based photocatalysts documented in the literature. Detailed mechanistic studies, aided by TAS, in situ X-ray photoelectron spectroscopy (XPS), and in situ electron paramagnetic resonance (EPR) techniques, indicate that the oxygen vacancies at the Ag-TiO2 interface act as an interfacial hole trap, inducing a directional hole transfer. This, coupled with Ag acting as an electron acceptor, synergistically boosts the electron-hole separation. Additionally, the increased amount of oxygen vacancies at the Ag-TiO2 interface of Ag/TiO2-50 leads to enhanced O2 adsorption, thus contributing to its superior catalytic performance. This study provides valuable insights into interfacial traps in the charge transfer process and highlights the potential of interface regulation for achieving efficient photocatalytic conversion.

A‐D‐A‐type Molecule with Dual Functions of Efficient Charge Extraction and Trap Passivation for n‐i‐p Perovskite Solar Cells

AbstractInterfacial defects and energy level mismatches between the perovskite and 2,2′,7,7′‐tetrakis[N,N‐di(4‐methoxyphenyl)amino]‐9,9′‐spirobifluorene (Spiro‐OMeTAD) layers heavily hinder charge transfer, limiting the efficiency and stability of n‐i‐p perovskite solar cells (PSCs). Herein, D‐type TPA, D‐A‐type TPA‐CN, and A‐D‐A‐type DTPA‐CN with triphenylamine units and different interfacial dipoles are designed as multifunctional interfacial layers for n‐i‐p PSCs. Among the three molecules, A‐D‐A‐type DTPA‐CN has the largest dipole moment, hole transporting capability, and hydrophobicity, and therefore the strongest passivation of interfacial defects and the best carrier extraction efficiency can be observed. As a result, the DTPA‐CN‐treated device achieves a champion power conversion efficiency (PCE) of 25.00%, as compared to the control device (22.78%). Moreover, the long‐term stability of the unencapsulated device is significantly improved. After 2,040 h of storage in a nitrogen glove box, the device maintains over 90% of its initial efficiency, while only 61% for the control device. The work indicates that simultaneous improvement of trap passivation and hole extraction is critical for achieving highly efficient and stable n‐i‐p PSCs.

Long-lived carriers-promoted photocatalytic deuteration of halides with D2O as the deuterium source over Cu doped quantum dots

Deuterium labeling is a highly valuable yet challenging subject of research in various scientific fields. Conventional deuteration methods often involve harsh reaction conditions and suffer from limited reactivity and selectivity. Herein, we report a visible light–driven C–X (X = halogen) to C–D (D = deuterium) exchange strategy over copper-doped cadmium sulfide quantum dots (Cu-CdS QDs) under mild conditions, eliminating the need for noble metal catalysts and expensive deuterium sources. The conversion of aryl halides into deuterated products using Cu-CdS QDs reaches up to 99%, which is four times higher than that achieved using pristine CdS QDs. The substantial enhancement in the photocatalytic activity of the QDs can be primarily attributed to the generation of long-lived charge carriers (approximately 6 μs) induced by Cu doping. Mechanistic studies reveal that the Cu dopants considerably retard the recombination of photoinduced carriers by creating intermediate energy levels that serve as hole trapping centers in CdS QDs, thereby improving the electron utilization efficiency in energetically demanding photoreduction reactions. Additionally, the introduction of Cu increases the energy offset between the conduction band of CdS QDs and molecular acceptors, facilitating the electron transfer process. Upon visible light irradiation, a series of aryl halides can be efficiently converted into the desired deuterated compounds using D2O as the deuterium source. This work demonstrates that regulating charge carrier dynamics in ultrasmall QD-based photocatalysts is a promising strategy for promoting organic transformations.

Comprehensive characterization of nitrogen-related defect states in β-Ga2O3 using quantitative optical and thermal defect spectroscopy methods

This study provides a comprehensive analysis of the dominant deep acceptor level in nitrogen-doped beta-phase gallium oxide (β-Ga2O3), elucidating and reconciling the hole emission features observed in deep-level optical spectroscopy (DLOS). The unique behavior of this defect, coupled with its small optical cross section, complicates trap concentration analysis using DLOS, which is essential for defect characterization in β-Ga2O3. A complex feature arises in DLOS results due to simultaneous electron emission to the conduction band and hole emission to the valence band from the same defect state, indicating the formation of two distinct atomic configurations and suggesting metastable defect characteristics. This study discusses the implications of this behavior on DLOS analysis and employs advanced spectroscopy techniques such as double-beam DLOS and optical isothermal measurements to address these complications. The double-beam DLOS method reveals a distinct hole emission process at EV+1.3 eV previously obscured in conventional DLOS. Optical isothermal measurements further characterize this energy level, appearing only in N-doped β-Ga2O3. This enables an estimate of the β-Ga2O3 hole effective mass by analyzing temperature-dependent carrier emission rates. This work highlights the impact of partial trap-filling behavior on DLOS analysis and identifies the presence of hole trapping and emission in β-Ga2O3. Although N-doping is ideal for creating semi-insulating material through the efficient compensation of free electrons, this study also reveals a significant hole emission and migration process within the weak electric fields of the Schottky diode depletion region.

Identification of shallow trap centers in InSe single crystals and investigation of their distribution: A thermally stimulated current spectroscopy

Identification of trap centers in semiconductors takes great importance for improving the performance of electronic and optoelectronic devices. In the present study, we employed the thermally stimulated current (TSC) method within a temperature range of 10–280 K to explore trap centers in InSe crystal—a material with promising applications in next-generation devices. Our findings revealed the existence of two distinct hole trap centers within the InSe crystal lattice located at 0.06 and 0.14 eV. Through the leveraging the Tstop method, we offered trap distribution parameters of revealed centers. The results obtained from the experimental methodology employed to investigate the distribution of trap centers indicated that one of the peaks extended between 0.06 and 0.13 eV, while the other spanned from 0.14 to 0.31 eV. Notably, our research uncovers a remarkable variation in trap density, spanning one order of magnitude, for every 10 and 88 meV of energy variation. The results of our research present the characteristics of shallow trap centers in InSe, providing important information for the design and optimization of InSe-based optoelectronic devices.

Charge Carrier Capture by Prominent Defect Centers in 4H-SiC

The knowledge of capture properties of electrically active defects is of primary importance as it helps to understand which deep states are effective in controlling the excess free carriers’ lifetime. Combining DLTS capture experiments with thermal emission measurements enables an overall thermodynamic description of deep states, thus making it possible to characterize recombination centers in semiconductor-based devices. In the present study, junction DLTS capture rate measurements were employed to extract the true capture cross-sections (inversely proportional to the carrier lifetime) and capture energy barriers for the main lifetime limiting defects in 4H-SiC (silicon carbide). A peculiar forward bias dependence of the capture parameters was observed for the shallow boron (B) hole trap. Capture rate measurements on the deep boron (D-center) trap also evidenced the presence of two capture mechanisms, thus allowing discrimination of D1 and D2 deep states within the D-center DLTS peak. The results were combined with activation energies and apparent capture cross-sections to obtain the free energy (ΔG) of electronic activation for the analysed deep states.

Demystifying Trion Emission in CdSe Nanoplatelets.

At cryogenic temperatures, the photoluminescence spectrum of CdSe nanoplatelets (NPLs) usually consists of multiple emission lines, the origin of which is still under debate. While there seems to be consensus that both neutral excitons and trions contribute to the NPL emission, the prominent role of trions is rather puzzling. In this work, we demonstrate that Förster resonant energy transfer in stacks of NPLs combined with hole trap states in specific NPLs within the stack trigger trion formation, while single NPL spectra are dominated by neutral excitonic emission. This interpretation is verified by implementing copper (Cu+) dopants into the lattice as intentional hole traps. Trion emission gets strongly enhanced, and due to the large amount of hole trapping Cu+ states in each single NPL, trion formation does not necessarily require stacking of NPLs. Thus, the ratio between trion and neutral exciton emission can be controlled by either changing the amount of stacked NPLs during sample preparation or implementing copper dopants into the lattice which act as additional hole traps.

(Invited) Luminescent InP Quantum Dots: They're Not Just Like CdSe

Time-resolved photoluminescence (PL) and transient absorption (TA) spectroscopy have been used to elucidate the electron and hole dynamics in high quality InP/ZnSe/ZnS quantum dots (QDs) at room temperature. These dynamics depend critically on the overall In:P ratio. Stoichiometric QDs (those having an In:P ratio close to unity), have PL quantum yields of > 90% and exhibit dynamics that are very simple: both electron and hole relaxation to the bandedge is fast compared to the ~ 40 ps time-correlated photon-counting instrument response and the PL follows a single exponential decay having a time constant of about 26 ns. However, QDs having an In:P ratio greater than about 1.1 maintain PL quantum yields > 90%, but show much more complicated PL kinetics. In the non-stoichiometric QDs, a significant fraction of the PL exhibits a slower risetime. The PL rises over a range of timescales varying from close to the instrument response to approximately 2.0 ns. The time constant of the slowest component increases with increasing InP core size and the fraction of the PL that has the slow risetime increases with excess indium in the particle. The slow risetime is absent in the TA results, indicating that the slow dynamics may be assigned to relaxation in the valence band. The risetime increases with the thickness of the ZnSe shell, varying from < 40 ps for the thinnest (1.1 nm) to about 2.0 ns for the thickest (2.7 nm) ZnSe shells. In addition to the slow risetime, the QDs having excess indium show a significant long-lived (>100 ns) decay component. The magnitude and time constant of this slow decay also increases with ZnSe shell thickness.These results suggest that holes are transiently trapped at sites associated with indium dopants in the ZnSe shell. The trapped hole has negligible overlap with the conduction band electron, making this an optically dark state. The holes are in an equilibrium between the shell traps and the valence band, giving rise to the delayed emission. Several possible assignments of the trapping species can be considered, and a substitutional indium adjacent to a zinc vacancy, In3+/VZn 2-, is the most likely. This assignment is consistent with the observation that trapping occurs only when the QD has excess indium and is supported by experiments showing that the addition of zinc oleate or acetate decreases the extent of trapping, presumably by filling some of the vacancy traps. Further experiments show that addition of alkyl carboxylic acids causes increased trapping, presumably by the formation of zinc oleate, thereby creating additional zinc vacancies. Chloride ion is a common impurity in the synthesis of InP/ZnSe/ZnS QDs and the possibility of In3+/Cl- impurities acting as the hole trap can be also considered. However, additional experimental data on InP/ZnSe/ZnS QDs synthesized in the absence of chloride show the same PL risetimes and delayed emission, eliminating this possibility. Density functional theory calculations further corroborate assignment of the trapping species to In3+/VZn 2-. These calculations show that either a single In2+ ion or an In2+-In3+ dimer is much too easily oxidized to form the reversible traps observed experimentally, while In3+ is far too difficult to oxidize. However, a zinc vacancy adjacent to a substitutional indium is calculated to have its highest occupied orbitals about 1 eV above the top of the valence band of bulk ZnSe, in the appropriate energy range to act as reversible traps for quantum confined holes in the InP valence band.

(Invited) Resolving Catalytic Mechanism at an Electrode Surface: Thermodynamics & Kinetics of Reaction Steps

Computationally, often the energetics of intermediate reaction steps differentiate the efficiency of heterogeneous catalysts for product evolution. Yet, when compared to experiment, kinetic models are applied. For example, a material’s activity measured by one rate of product evolution is plotted as a function of the calculated formation energies of intermediate chemical forms. A critically important reaction for which this dichotomy between experiment and theory exists is the oxygen evolution reaction (OER) from water. In the laboratory group, we employ time-resolved optical and vibrational spectroscopy to deconstruct OER into its individual reaction steps on an electrode surface. In the presentation, I will describe the experimental methodology and the chosen model system, the n-doped SrTiO3/aqueous interface. I’ll show how these experiments identify both the rates and energetics of the first reaction step, the release of a proton and electron from an absorbed water species, denoted by OH* or O*. A recent success was to isolate a Langmuir isotherm of the intermediate population arising within < 2 ps on the SrTiO3 surface. The intermediate population is of trapped holes measured by emission from the conduction band into unoccupied states in the middle of the semi-conductor bandgap. The isotherm is tuned by the pH of the electrolyte. The pH-dependent formation of these intermediates are connected to their pH-dependent decay at microsecond timescales, presumably related to later reaction steps of OER. I'll also present work on the side of vibrational spectroscopy that looks at how the potential energy surface of a particular trapped hole, the terminal oxyl radical, arises in time through the spectral kinetics of its normal mode. A growing area is to apply the particular experimental methodology to a surface of similar electronic structure but diverse crystal geometries, namely polymorphs of TiO2.

(Keynote) Light Driven H2 Generation in Pt-Tipped CdS Nanorods: Dependence on the Pt Size and CdS Rod Length

Colloidal quantum confined semiconductor-metal nano-heterostructures are a promising class of photocatalysts for solar energy conversion. In these photocatalysts, the semiconductor domain serves as the light absorber and the metal as the catalyst. Such photocatalysts combine the superior light absorption and charge transport properties of the semiconductor with the superior catalytic activity and selectivity of the metal. Furthermore, both domains can be independently tuned to enhance the photocatalytic performance of the heterostructure. Among various semiconductor/metal heterostructures, metal-tipped colloidal semiconductor nanorods have attracted extensive interest because they have been reported to have high quantum efficiencies of light driven H2 generation and their morphology can be systematically tuned. The overall light driven H2 generation process involves multiple elementary charge separation and recombination steps in the semiconductor and across the semiconductor/metal interface as well as proton-coupled electron transfer reactions at the catalytic center. The change of the semiconductor or metal domains can often have effects on multiple competing processes involved in the overall reaction. As a result of these complexities, the mechanisms for the morphological dependence of the observed H2 generation efficiencies are not fully understood, hindering the rational design of these photocatalysts. In this talk, we use Pt tipped CdS nanorods (CdS-Pt) as a model system to examine the effect of Pt size and CdS rod length on their light driven H2 generation efficiency. We show that increasing the Pt particle size increases the overall H2 generation quantum efficiency through both increasing the rate of electron transfer from the CdS to Pt and enhancing the efficiency of water/proton reduction; H2 generation efficiency increases at longer CdS rod length by suppression of charge recombination across the Pt/CdS interface. Furthermore, because of rapid trapping of valence band holes, multi-exciton states in CdS nanorods can be long lived, enabling efficient multi-electron transfer to the Pt. Our work demonstrates that through systematic in situ study of elementary processes involved in the overall H2 generation, it is possible to rationally design and improve semiconductor-metal hybrid photocatalysts.