Boron Acceptors Research Articles

Acceptor-Induced Bulk Dielectric Loss in Superconducting Circuits on Silicon

The performance of superconducting quantum circuits is primarily limited by dielectric loss due to interactions with two-level systems (TLSs). State-of-the-art circuits with engineered material interfaces are approaching a limit where dielectric loss from bulk substrates plays an important role. However, a microscopic understanding of dielectric loss in crystalline substrates is still lacking. In this work, we show that boron acceptors in silicon constitute a TLS bath that leads to an energy dissipation channel for superconducting circuits. We discuss how the electronic structure of boron acceptors leads to an effective TLS response in silicon. We sweep the boron concentration in silicon and demonstrate the bulk dielectric loss limit from boron acceptors. We show that boron-induced dielectric loss can be reduced in a magnetic field due to the spin-orbit structure of boron. This work provides the first detailed microscopic description of a TLS bath for superconducting circuits and demonstrates the need for ultrahigh-purity substrates for next-generation superconducting quantum processors. Published by the American Physical Society 2024

Differences in carbonyl groups and boron acceptors in MR‐TADF and full‐color emission merging strategies: A theoretical study

AbstractMulti‐resonant thermally activated delayed fluorescent (MR‐TADF) materials, which combine large oscillator strengths, small singlet‐triplet energy gaps, high photoluminescence quantum yields, and color purity, have attracted great interest in both experimental and theoretical research in recent years. However, the differences between two classes of MR‐TADF, utilizing carbonyl groups and boron atoms as acceptors respectively, have not been clearly delineated, and the implementation of strategies combining both is extremely limited. This limitation hampers the diversity in composition and structure of MR‐TADF. In this study, we employed boron as the central acceptor and carbonyl groups as peripheral acceptors, designing and investigating 7 merged systems of MR‐TADF molecules. Calculations revealed that, in contrast to the strong acceptor characteristics of boron atoms, carbonyl groups do not exhibit absolute acceptor features, and their resonance effects depend on the surrounding environment. This unique resonance effect induces LRCT features to varying degrees, enabling the emission coverage of these molecules across almost the entire visible spectrum (theoretical emission wavelengths covering 452–751 nm). We gained an understanding of the differences between boron acceptors and carbonyl groups, achieving full‐color emission by adjusting only the MR cores. This provides insights into the rational design of complex‐component full‐color MR‐TADF emitters.

Improving efficiency in RGB phosphorescent and white organic light emitting diodes via donor-spiro-boron acceptor host materials

The universal host material with boron acceptor core structure is exceptionally sparse to be designed for red, green, and blue in efficient phosphorescent organic light emitting diodes (PhOLEDs) accompanying white OLEDs, possessing indistinguishable device feature. Herein, two boron acceptors spiro-host materials namely 1'-(4-(dimesitylboranyl)phenyl)-10-phenyl-10H-spiro[acridine-9,9′-fluorene] (TPA-PBM) and 1-(4-(dimesitylboranyl)phenyl)-3′,6′-dimethylspiro[fluorene-9,8′-indolo[3,2,1-de]acridine] (2MeCz-PBM) were designed and synthesized. The designed rigid donor strategy exhibited good device performance among the reported boron donor-spiro-acceptor (D-spiro-A) skeleton for organic light emitting diodes (OLEDs). In particular, we fabricate RGB three-color phosphorescent OLEDs based on TPA-PBM and 2MeCz-PBM. The red devices exhibit a maximum external quantum efficiency (EQE) of nearly 28 % (26.8 % for TPA-PBM and 27.5 % for 2MeCz-PBM), with an electroluminescence spectrum at 608 nm. The green/blue devices obtain maximum EQEs of 21.2 %/15.3 % and 21.8 % 17.3 %, for TPA-PBM and 2MeCz-PBM, respectively. Furthermore, green devices display an extremely low efficiency roll-off with decreasing 1 % and 3 % at luminance of 5000 cd m−2. Additionally, the two-color white OLED using 2MeCz-PBM exhibits EQEmax and PEmax are 24.5 % and 62.9 lm W−1 respectively, the EQE remain 23.8 % at commercial lighting brightness of 1000 cd m−2. The WOLED also shows a stable white spectrum with CIE varying range of (0.41, 0.47) to (0.39, 0.46) at 100 cd m−2 to 15000 cd m−2. All obtained results confirmed that our targeted molecules have advantage of carrier balance and efficient charge recombination, which might replace many other commercial host materials.

Multifunctional Deep-Blue Thermally Activated Delayed Fluorescence Based on an Oxygen-Bridged Boron Acceptor for Highly Efficient Organic Light-Emitting Diodes.

Until now, thermally activated delayed fluorescence (TADF) materials based on bridged boron-based acceptors have been primarily developed as dopants. However, in this study, we synthesized and characterized multifunctional deep-blue TADF materials─t-OBO-DMAC and t-OBO-DPAC─using bridged boron-based acceptors in combination with dimethylacridine or diphenylacridine as donors. These materials serve as both dopants and hosts. Theoretical calculations and experimentally measured photophysical properties of t-OBO-DMAC reveal a smaller singlet-triplet energy difference, higher photoluminescence quantum yield, and more efficient reverse intersystem crossing compared to t-OBO-DPAC. When evaluated as TADF emitters, t-OBO-DMAC and t-OBO-DPAC exhibited maximum external quantum efficiency (EQE) of 14.4 and 7.3% with deep-blue color coordinates of (0.14, 0.11) and (0.15, 0.07), respectively. Both materials were further assessed as hosts in various configurations, including host-only, TADF, phosphorescent, and phosphor-sensitized fluorescence (PSF)-emitting systems. Notably, t-OBO-DMAC demonstrated a high maximum EQE of 13.9% with deep-blue color coordinates of (0.15, 0.07) in a nondoped host-only device. Remarkably, both materials achieved EQEs exceeding 20% in the PSF devices. Our study marks a critical advancement in the field that breaks the conventional boundaries of the dopant and host and demonstrates unprecedented multifunctionalities for advanced organic light-emitting diodes.

Thermally activated delayed fluorescence emitters with bulky four-coordinate boron acceptors for high-performance solution-processed OLEDs

Although considerable progress has been made in vacuum-deposited thermally activated delayed fluorescence (TADF) organic light-emitting diodes (OLEDs), the development of inexpensive solution-processed TADF-OLEDs still lags, primarily owing to low luminous efficiency. Herein, we designed and synthesized two TADF emitters by introducing bulky four-coordinate boron into pyrimidine acceptor, producing a simple and versatile approach to dramatically enhance performance. The introduction of bulky four-coordinate boron substantially reduces the singlet–triplet energy gap and improves photoluminescent quantum yield as well as improves solubility by inhibiting intermolecular aggregation or crystallization, resulting in an excellent TADF characteristics and highly efficient solution-processed OLEDs. Finally, the Spiro-PMB-SPAc emitter provides an OLED device with a remarkable maximum external quantum efficiency of 38.21 %, which reaches 32.50 % at a luminance of 500 cd m−2. This state-of-the-art performance validates the superiority of the boron-nitrogen coordination strategy in the reconstruction of pyrimidine-based TADF molecules for highly efficient solution-processed OLEDs.

Optimization of Activation Annealing Condition for Boron‐Implanted Diamond

Impurity activation of dopants implanted in diamond is one of the crucial issues for device application of diamond. Boron impurity atoms are introduced in diamond, which expectedly act as acceptors, by ion implantation technique, and are investigated the optimum annealing time for the effective dopant activation. The impurity doping is performed by boron ion implantation at multiple incident energies to obtain a uniform dopant concentration from the surface to 350 nm depth followed by activation annealing at 1300 °C for 5–240 min. The electrical properties of specific resistance, carrier concentration, and conduction type are analyzed as a function of temperature from room temperature to 873 K. The estimated ionization energy is strongly dependent on the annealing time and asymptotically approaches to 0.3 eV, which is theoretically expected ionization energy of acceptor boron, with increasing annealing time. A shorter annealing time ( does not sufficiently recover radiation damages caused by ion implantation forming deep levels, which act as irregular conduction. It is consequently found that an optimum window of annealing time for effective dopant activation and suggested carrier transport mechanisms depending on the annealing time.

Interactions of hydrogen atoms with boron and gallium in silicon crystals co-doped with phosphorus and acceptors

Reports showing that hydrogen and group-III acceptors play an important role in Light- and elevated Temperature-induced Degradation (LeTID) of Si-based solar cells highlight the need for a better understanding of interactions between these two species. In this contribution, a combination of junction spectroscopy techniques and first principles modelling has been used to study hydrogen-induced changes in electrical properties of either boron or gallium Czochralski-grown silicon co-doped with phosphorus in order to produce n-type material facilitating novel techniques to assess recombination active defects. The interactions of hydrogen with acceptor atoms have been induced via annealing of these co-doped hydrogenated samples with the application of reverse bias (RBA). These treatments have resulted in a significant increase in the net shallow donor concentration in depletion regions of both materials and in the appearance of a strong electron emission signal due to a trap with an energy level at about Ec −0.18 eV in the DLTS spectra of Si:P + B material. It is argued that this trap is related to the donor level of a BH2 complex. Calculations using density functional theory have shown that the BH2 defect has a charge-state dependent geometry, which turns out to be crucial for the proposed non-radiative recombination mechanism. The BH2 defect is therefore suggested to be the root cause of LeTID in boron-doped Si. In contrast, modelling results predict that GaH2 is a defect with shallow energy levels, without the characteristic features of a recombination centre. This is corroborated by the results of electrical measurements on hydrogenated Si:P + Ga subjected to RBA. Conventional annealing treatments were subsequently used to assess the thermal stability of acceptor-H related defects. Based on the obtained results, the peculiarities of hydrogen interactions with boron and gallium acceptors are discussed.

Single-Charge Tunneling in Codoped Silicon Nanodevices.

Silicon (Si) nano-electronics is advancing towards the end of the Moore's Law, as gate lengths of just a few nanometers have been already reported in state-of-the-art transistors. In the nanostructures that act as channels in transistors or depletion layers in pn diodes, the role of dopants becomes critical, since the transport properties depend on a small number of dopants and/or on their random distribution. Here, we present the possibility of single-charge tunneling in codoped Si nanodevices formed in silicon-on-insulator films, in which both phosphorus (P) donors and boron (B) acceptors are introduced intentionally. For highly doped pn diodes, we report band-to-band tunneling (BTBT) via energy states in the depletion layer. These energy states can be ascribed to quantum dots (QDs) formed by the random distribution of donors and acceptors in such a depletion layer. For nanoscale silicon-on-insulator field-effect transistors (SOI-FETs) doped heavily with P-donors and also counter-doped with B-acceptors, we report current peaks and Coulomb diamonds. These features are ascribed to single-electron tunneling (SET) via QDs in the codoped nanoscale channels. These reports provide new insights for utilizing codoped silicon nanostructures for fundamental applications, in which the interplay between donors and acceptors can enhance the functionalities of the devices.

Achieving over 36% EQE in blue OLEDs using rigid TADF emitters based on spiro-donor and spiro-B-heterotriangulene acceptors

The design of robust thermally activated delayed fluorescence (TADF) emitters is crucial in realizing highly efficient and stable blue TADF-organic light-emitting diodes (OLEDs). Here boron-based donor–acceptor-type blue TADF compounds incorporating a triply-bridged, spiro-type boron acceptor; namely, spiro-fluorenyl B-heterotriangulene, and 9,9-diphenyl-9,10-dihydroacridine (DPAC, 1) or 10H-spiro[acridine-9,9′-fluorene] (sAC, 2) donors are presented. Their doped host films show blue emissions with narrow full width at half maximum values of 52 nm (0.29 eV) and unitary photoluminescence quantum yields. The compounds exhibit short-lived delayed fluorescence (τd = 1.8–2.7 μs) and undergo fast reverse intersystem crossing with the rate constants of ∼106 s−1 in the film state. These are attributable to the small singlet–triplet energy splitting of ∼40 meV and the effective spin–orbit coupling between the singlet (1CT, S1) and local triplet (3LE, T2) excited states. From outstanding horizontal transition dipole orientation ratios of 0.89 and 0.90 for the host films of 1 and 2, respectively, high-efficiency blue TADF-OLEDs showing maximum external quantum efficiencies (EQEs) of over 30% are realized. Notably, the device with the fully spiro 2 achieves a state-of-the-art EQEmax of 36.4% and a suppressed efficiency roll-off, with a high EQE of 26.3% even at 1,000 cd/m2, highlighting the synergistic effect between the spiro-structure and the B-heterotriangulene acceptor skeleton.

Coherent coupling of metamaterial resonators with dipole transitions of boron acceptors in Si.

We investigate the coherent coupling of metamaterial resonators with hydrogen-like boron acceptors in Si at cryogenic temperatures. When the resonance frequency of the metamaterial, chosen to be in the range 7-9 THz, superimposes the transition frequency from the ground state of the acceptor to an excited state, Rabi splitting as large as 0.4 THz is observed. The coherent coupling shows a feature of cooperative interaction, where the Rabi splitting is proportional to the square root of the density of the acceptors. Our experiments may help to open a possible route for the investigation of quantum information processes employing strong coupling of dopants in cavities.

Hydrogen effects at sputtered Tb-doped AlNxOy:H / c-Si(p) interfaces: A transient surface photovoltage spectroscopy study

In the present work, we studied the interface of terbium doped aluminum oxynitride (Tb-doped AlNxOy:H) deposited under different hydrogen flows with p-type doped crystalline silicon by applying transient surface photovoltage spectroscopy. We observed strong accumulation with concomitant passivation of boron acceptors in the crystalline silicon and defect generation near the interface. With increasing hydrogen flows, the net negative charge in the Tb-doped AlNxOy:H layer decreased, surface photovoltage signals related to defects increased, surface photovoltage transients decayed faster, and the slowest relaxation of charge carriers separated in space changed from trap limited to hopping transport via an exponential distribution of trap states in energy.

The effect of boron concentration on the electrical, morphological and optical properties of boron-doped nanocrystalline diamond sheets: Tuning the diamond-on-graphene vertical junction

In this paper, the effect of boron doping on the electrical, morphological and structural properties of free-standing nanocrystalline diamond sheets (thickness ~ 1 μm) was investigated. For this purpose, we used diamond films delaminated from a mirror-polished tantalum substrate following a microwave plasma-assisted chemical vapor deposition process, each grown with a different [B]/[C] ratio (up to 20,000 ppm) in the gas phase. The developed boron-doped diamond (BDD) films are a promising semiconducting material for sensing and high-power electronic devices due to band gap engineering and thermal management feasibility. The increased boron concentration in the gas phase induces a decrease in the average grain size, consequently resulting in lower surface roughness. The BDD sheets grown with [B]/[C] of 20,000 ppm reveal the metallic conductivity while the lower doped samples show p-type semiconductor character. The charge transport at room temperature is dominated by the thermally activated nearest-neighbor hopping between boron acceptors through impurity band conduction. At low temperatures (<300 K), the Arrhenius plot shows a non-linear temperature dependence of the logarithmic conductance pointing towards a crossover towards variable range hopping. The activation energy at high temperatures obtained for lowly-doped sheets is smaller than for nanocrystalline diamond bonded to silicon, while for highly-doped material it is similar. Developed sheets were utilized to fabricate two types of diamond-on-graphene heterojunctions, where boron doping is the key factor for tuning the shape of the current-voltage characteristics. The graphene heterojunction with the low boron concentration diamond sheet resembles a Schottky junction behavior, while an almost Ohmic contact response is recorded with the highly doped BDD sheet of metallic conductivity. The free-standing diamond sheets allow for integration with temperature-sensitive interfaces (i.e. 2D materials or polymers) and pave the way towards flexible electronics devices.

Highly Efficient Blue Thermally Activated Delayed Fluorescence Emitters Based on Multi-Donor Modified Oxygen-Bridged Boron Acceptor.

The employment of thermally activated delayed fluorescence (TADF) emitters is one of the most promising ways to realize the external quantum efficiency (EQE) of over 25% for organic light-emitting diodes (OLEDs). In addition, the TADF emitter based on oxygen-bridged boron (BO) fragment can maintain blue emission with high color purity. Herein, we constructed two blue TADF emitters, 3TBO and 5TBO, for OLEDs application. Both emitters consist of three donors linked at the oxygen-bridged boron acceptor. OLED devices based on 3TBO and 5TBO exhibited both high excellent device efficiency and high color purity with a maximum EQE; full-width at half-maximum (FWHM); and CIE coordinates of 17.3%, 47 nm, (0.120, 0.294), and 26.2%, 57 nm, (0.125, 0.275), respectively.

On the kinetics of the exchange of hydrogen between hydrogen–boron pairs and hydrogen dimers in crystalline silicon

Silicon samples after fast-firing with a hydrogen-rich silicon nitride layer on their surfaces can contain high concentrations of hydrogen (up to 6 × 1015 cm−3 in this study). Directly after fast-firing, this hydrogen is mostly present in a neutral dimeric state. Subsequent dark annealing applied in a temperature range between 140 and 175 °C leads to a conversion of dimers into HB pairs, which means that a significant number of boron acceptors are electrically inactive. The concentration of inactive boron, the hydrogen–boron (HB) pair concentration [HB], can thus be determined by measuring the change in specific resistivity before and after annealing. In our study, after the initial anneal for HB pair formation, the same samples are subsequently annealed at stepwise increasing higher temperatures, which leads to a partial backward conversion of HB pairs into neutral hydrogen dimers. This is indicated by a gradual reduction of the resistivity upon increasing the annealing temperature. By measuring the transient curves [HB](t) during each temperature step on samples with different boron content, we extract the parameters for the exchange between the HB pairs and the hydrogen dimers within the framework of our presented physical model. Apart from the backward formation of hydrogen dimers, from HB pairs upon increasing temperature, prolonged annealing at the same temperature leads to a transition of HB pairs into a more stable form of hydrogen dimers, compared to the initial form after fast-firing. This transition is also included in our proposed defect model.

Electron paramagnetic resonance study of silicon-28 single crystal for realization of the kilogram

To realize the kilogram with high accuracy using the x-ray crystal density method, mass deficit correction to account for the number of vacancy defects in silicon-28 crystals is necessary. In this paper, we present the results of electron paramagnetic resonance (EPR) spectroscopy experiments performed on a silicon-28 crystal. The crystal was cut from near the radial center of the Si28–23Pr11 crystal boule where a relatively high vacancy defect concentration was expected within the boule, which was grown by the floating zone method. We obtained both the in-phase and out-of-phase EPR spectra, which focused on the fast- and slow-spin relaxation centers, respectively. Based on EPR measurements both in the dark and under illumination, the concentrations of phosphorus impurities with unpaired electrons were found to be between 1.6 × 1012 cm−3 and 3.4 × 1012 cm−3. In contrast, EPR-active vacancy defects in the silicon-28 crystal were not detected at the detection sensitivity of the present measurements (around 1 × 1012 cm−3), although at the Si/SiO2 interface, dangling-bond defects (P b0 centers) were detected with an areal density between 0.4 × 1012 cm−2 and 1.7 × 1012 cm−2. The experimental detection of a larger amount of phosphorus donors under illumination indicates the presence of compensation centers (electronic levels acting as acceptors) with a concentration of at most 1.6 × 1012 cm−3. We determined that such a concentration is mainly compensated by the boron acceptors, and that there is little contribution of electrically active vacancy defects, 0.0(6) × 1012 cm−3. This value is much smaller than the previously reported concentrations of 1 × 1014 cm−3 to 4 × 1014 cm−3 for vacancy defects determined by positron annihilation spectroscopy.

Polycyclic phenazine-derived rigid donors construct thermally activated delayed fluorescence emitters for highly efficient orange OLEDs with extremely low roll-off

Two new thermally activated delayed fluorescence (TADF) molecules, tBuInPz-BO and InPz-BO, are constructed via connecting novel rigid polycyclic phenazine-derived donors with oxygen-bridged boron acceptor. Both emitters exhibit fast reverse intersystem crossing rates and high photoluminescence quantum yields, owing to the high molecular structural rigidity. As a result, the orange organic light-emitting diode (OLED) fabricated with tBuInPz-BO shows a maximum external quantum efficiency (EQEmax) of 22.0% with the electroluminescence peak at 585 nm. Moreover, the device displays extremely low efficiency roll-off. At high luminance of 1000 and 10000 cd/m2, the EQE values still maintain a high level of 20.2% and 14.8%, respectively, achieving state-of-the-art electroluminescence performance among TADF-based orange OLEDs. This work reveals the great potential of the new phenazine-derived donors for constructing highly efficient TADF emitters.

Multiple charge transfer disk-like emitters with fast fluorescence radiation rate and high horizontal dipole orientation for pure blue organic light-emitting diodes

• Multiple CT channels and 3 LE states contribute to the speedy k r and RISC processes. • High Θ and small FWHM are realized due to the rigid disk-like structure. • η r and η out above 30% are achieved owing to triplet exciton utilization and high Θ . • EQE above 10% was realized for the standard blue device based on BO3N. The efficiency of pure blue Organic light-emitting diodes (OLEDs) still needs to be improved, which is limited by the utilization of the forbidden transition triplet excitons and low light-out-coupling efficiency in devices. Herein, two blue emitters were developed through combining multiple diphenylamine (DPA) donors with an oxygen-bridged boron (DBA) or triphenyl triazine (TRZ) acceptor. Notably, a narrow-band deep blue emission with a peak of 423 nm and a Full-width at half-maximum (FWHM) of 34 nm is realized for the boron-based emitter in toluene solution. Thanks to their multiple Charge transfer (CT) channels and high orientated disk-like structure, high radiative transition rates ( k r > 10 8 s −1 ) and high horizontal emitting dipole ratios ( Θ > 80%) can be realized simultaneously. Meanwhile, the introduction of the peripheral DPA units can also provide multiple localized triplet ( 3 LE) states for spin up-conversion of forbidden transition triplet excitons. Owing to the effective up-conversion of triplet excitons and high light-out-coupling efficiency, maximum external quantum efficiency of more than 10% is achieved for the boron emitter-based pure blue OLEDs with a Commission Internationale de l’Eclairage (CIE) coordinates of (0.14, 0.08).

Charge stability of shallow single nitrogen-vacancy centers in lightly boron-doped diamond

Nitrogen vacancy (NV) centers in diamond must be in a stable negatively charged state for their application to quantum sensing and quantum information processing. In this study, we investigated the charge-state stability of single NV centers in lightly boron-doped diamond ([B] ≈ 1 × 1015 cm−3). Photoluminescence and optically detected magnetic resonance measurements indicated that single NV centers near the diamond surface are negatively charged despite the presence of boron acceptors. This unique phenomenon can be explained by charge transfer between the NV centers and their local environment under laser excitation. This study provides a new perspective on the charge stability of single NV centers in lightly doped diamond and insights for further development of high-performance diamond quantum devices.

Synthesis of 3,6,8,11-tetramethyl-5H,9H-quino[3,2,1-de]acridine-5,9-dione

The latest progress in the construction of organic light-emitting diodes (OLEDs) has created a demand for the development of new, convenient and efficient methods of synthesis of completely organic phosphors with an elongated π-system and a set of electrochemical and photophysical properties. Nowadays, the last generation of organic emitters for high-performance OLEDs is materials that demonstrate thermally activated delayed fluorescence (TADF) phenomenon. Such materials can convert into light energy, both emitting singlet and dark triplet excitons and, thus, the internal efficiency of OLEDs, based on such compounds, reaches 100 %. Two main approaches have been developed for a targeted synthesis of organic TADF materials. The first and most studied of these is the synthesis of donor-acceptor conjugates, in which the donor and acceptor units are placed relative to each other at a significant angle, close to 90°. The second approach to the molecular design of TADF materials is to construct polynuclear heterocyclic compounds with a rigid framework, in which HOMO and LUMO are localized on the atoms of the cycles through one. The first example of a successful implementation of such strategy was the boro-azo-heterocyclic compound DABNA-1, the synthesis and characterization of which was first published in 2016. It was later discovered that boron acceptor atoms in the design of such compounds can be successfully replaced by carbonyl moieties, and, thus, it can simplify the synthesis and design of such compounds. Therefore, the attention of researchers was attracted by 5 H ,9 H -quino[3,2,1-de]acridine-5,9-dione heterocyclic system. The Ullmann reaction between 3,5-dimethyl-2,6-dicyanoaniline and 4-iodotoluene gave 2- (bis(4-methylphenyl)amino)-4,6-dimethylisophthalonitrile, which was heated in polyphosphoric acid for 4 hours. As a result intramolecular electrophilic cyclization involving both nitrile groups with the formation of 3,6,8,11-tetramethyl-5 H ,9 H -quino[3,2,1-de]acridine-5,9-dione take place. Keywords: 3,5-dimethyl-2,6-dicyanoaniline, 5H,9H-quino[3,2,1-de]acridine-5,9-dione, Ullmann reaction, cyclization, polyphosphoric acid.

Intraband Spin-Dependent Recombination of Bound Holes in Silicon.

We generate paramagnetic centers on a heavily boron-doped Si(111) surface by using a scanning tunneling microscope and show that they mediate the spin-dependent recombination of the bound holes of the boron acceptor via direct visualization. This recombination is the intraband process and is significantly affected by the spin-orbit coupling effect. We also demonstrate that such a paramagnetic center with a boron acceptor at its neighbor site can be produced with atomic precision, which makes it a promising candidate for implementing position-controlled impurity qubits with an electrical readout mechanism in silicon.