skip to main content

Attention:

The NSF Public Access Repository (NSF-PAR) system and access will be unavailable from 11:00 PM ET on Thursday, October 10 until 2:00 AM ET on Friday, October 11 due to maintenance. We apologize for the inconvenience.


Title: Inorganic Halide Perovskitoid TlPbI 3 for Ionizing Radiation Detection
Abstract

Room temperature semiconductor detector (RTSD) materials for γ‐ray and X‐ray radiation are in great demand for the nonproliferation of nuclear materials as well as for biomedical imaging applications. Halide perovskites have attracted great attention as emerging and promising RTSD materials. In this contribution, the material synthesis, purification, crystal growth, crystal structure, photoluminescence properties, ionizing radiation detection performance, and electronic structure of the inorganic halide perovskitoid compound TlPbI3are reported on. This compound crystallizes in the ABX3non‐perovskite crystal structure with a high density ofd = 6.488 g·cm–3, has a wide bandgap of 2.25 eV, and melts congruently at a low temperature of 360 °C without phase transitions, which allows for facile growth of high quality crystals with few thermally‐activated defects. High‐quality TlPbI3single crystals of centimeter‐size are grown using the vertical Bridgman method using purified raw materials. A high electrical resistivity of ≈1012 Ω·cm is readily obtainable, and detectors made of TlPbI3single crystals are highly photoresponsive to Ag KαX‐rays (22.4 keV), and detects 122 keV γ‐rays from57Co radiation source. The electron mobility‐lifetime productµeτewas estimated at 1.8 × 10–5cm2·V–1. A high relative static dielectric constant of 35.0 indicates strong capability in screening carrier scattering and charged defects in TlPbI3.

 
more » « less
NSF-PAR ID:
10452537
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Functional Materials
Volume:
31
Issue:
13
ISSN:
1616-301X
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Lead halide perovskites have recently attracted intensive attention as competitive alternative candidates of legacy compound materials CdTe, CdZnTe, and TlBr for high sensitivity energy‐resolving gamma‐ray detection at room temperature. However, the use of lead in these lead halide perovskites, which is necessary for increasing the stopping power of gamma radiation, poses a serious environmental concern due to the high toxicity of lead. In this regard, environmental‐friendly perovskite‐based gamma‐ray detector materials with key energy‐resolving capabilities are highly desired. Here, the gamma energy‐resolving performance of a new class of all‐inorganic and lead‐free Cs2AgBiBr6double perovskite single crystals (SCs) is reported. Two types of Cs2AgBiBr6SCs, prepared by Bi‐normal and Bi‐poor precursor solutions, respectively, have been grown. Their mobilities and response to gamma radiation are presented. Density of trap states in Bi‐poor Cs2AgBiBr6SCs (2.65 × 109 cm−3) is one order of magnitude lower than that in Bi‐normal Cs2AgBiBr6SCs (3.85 × 1010 cm−3). Using laser‐induced photocurrent measurements, the obtained mobility–lifetime (μ–τ) product in Bi‐poor Cs2AgBiBr6SCs is 1.47 × 10−3 cm2 V−1, indicating their great potentials for gamma‐ray detection. Further, the fabricated detector based on Bi‐poor Cs2AgBiBr6SC shows response to 59.5 keV gamma‐ray with an energy resolution of 13.91%.

     
    more » « less
  2. Abstract

    The wide‐bandgap, semiconducting ternary compound Hg3Se2I2has shown promise as room‐temperature hard‐radiation detector. Since this compound was first reported, there has been significant improvement in crystal growth using a chemical vapor transport method with a polyethylene growth agent. To study the effects of this additional precursor on crystal quality, the nature of radiative and nonradiative defects using photoluminescence (PL) and photocurrent (PC) studies of Hg3Se2I2single crystals are investigated. In contrast to earlier studies, excitation intensity‐dependence of PL emission shows that the near‐band‐edge (NBE) emission bands are all excitonic in nature. The PL intensity decreases with increasing temperature, with the higher energy peaks quenching by 40 K and the deeper levels quenched after 110 K. The PC spectra show a complex structure at room temperature related to NBE transitions in the band structure, while at low temperature only the direct gap transition is observed due to phonons freezing out. The PC spectra at low temperature also indicate several midgap levels that are attributed to native defects within the bulk crystal. These results indicate that the high quality of Hg3Se2I2single crystals is maintained when the transport agent is used during growth, although there are still a variety of defects present.

     
    more » « less
  3. Abstract

    Polarimetric infrared (IR) detection bolsters IR thermography by leveraging the polarization of light. Optical anisotropy, i.e., birefringence and dichroism, can be leveraged to achieve polarimetric detection. Recently, giant optical anisotropy is discovered in quasi‐1D narrow‐bandgap hexagonal perovskite sulfides, A1+xTiS3, specifically BaTiS3and Sr9/8TiS3. In these materials, the critical role of atomic‐scale structure modulations in the unconventional electrical, optical, and thermal properties raises the broader question of the nature of other materials that belong to this family. To address this issue, for the first time, high‐quality single crystals of a largely unexplored member of the A1+xTiX3(X = S, Se) family, BaTiSe3are synthesized. Single‐crystal X‐ray diffraction determined the room‐temperature structure with theP31cspace group, which is a superstructure of the earlier reportedP63/mmcstructure. The crystal structure of BaTiSe3features antiparallelc‐axis displacements similar to but of lower symmetry than BaTiS3, verified by the polarization dependent Raman spectroscopy. Fourier transform infrared (FTIR) spectroscopy is used to characterize the optical anisotropy of BaTiSe3, whose refractive index along the ordinary (Ec) and extraordinary (Ec) optical axes is quantitatively determined by combining ellipsometry studies with FTIR. With a giant birefringence Δn∼ 0.9, BaTiSe3emerges as a new candidate for miniaturized birefringent optics for mid‐wave infrared to long‐wave infrared imaging.

     
    more » « less
  4. Abstract

    Spectroscopic‐grade single crystal detectors can register the energies of individual X‐ray interactions enabling photon‐counting systems with superior resolution over traditional photoconductive X‐ray detection systems. Current technical challenges have limited the preparation of perovskite semiconductors for energy‐discrimination X‐ray photon‐counting detection. Here, this work reports the deployment of a spectroscopic‐grade CsPbBr3Schottky detector under reverse bias for continuum hard X‐ray detection in both the photocurrent and spectroscopic schemes. High surface barriers of1 eV are formed by depositing solid bismuth and gold contacts. The spectroscopic response under a hard X‐ray source is assessed in resolving the characteristic X‐ray peak. The methodology in enhancing X‐ray sensitivity by controlling the X‐ray energies and flux, and voltage, is described. The X‐ray sensitivity varies between a few tens to over 8000 μC Gyair−1cm−2. The detectable dose rate of the CsPbBr3detectors is as low as 0.02 nGyairs−1in the energy discrimination configuration. Finally, the unbiased CsPbBr3device forms a spontaneous contact potential difference of about 0.7 V enabling high quality of the CsPbBr3single crystals to operate in “passive” self‐powered X‐ray detection mode and the X‐ray sensitivity is estimated as 14 μC Gyair−1cm−2. The great potential of spectroscopic‐grade CsPbBr3devices for X‐ray photon‐counting systems is anticipated in this work.

     
    more » « less
  5. Abstract

    The dearth of suitable materials significantly restricts the practical development of infrared (IR) laser systems with highly efficient and broadband tuning. Recently, γ‐NaAsSe2is reported, and it exhibits a large nonlinear second‐harmonic generation (SHG) coefficient of 590 pm V−1at 2 µm. However, the crystal growth of γ‐NaAsSe2is challenging because it undergoes a phase transition to centrosymmetric δ‐NaAsSe2. Herein, the stabilization of non‐centrosymmetric γ‐NaAsSe2by doping the As site with Sb, which results in γ‐NaAs0.95Sb0.05Se2is reported. The congruent melting behavior is confirmed by differential thermal analysis with a melting temperature of 450 °C and crystallization temperature of 415 °C. Single crystals with dimensions of 3 mm × 2 mm are successfully obtained via zone refining and the Bridgman method. The purification of the material plays a significant role in crystal growth and results in a bandgap of 1.78 eV and thermal conductivity of 0.79 Wm−1K−1. The single‐crystal SHG coefficient of γ‐NaAs0.95Sb0.05Se2exhibits an enormous value of |d11| = 648 ± 74 pm V−1, which is comparable to that of γ‐NaAsSe2and ≈20× larger than that of AgGaSe2. The bandgap of γ‐NaAs0.95Sb0.05Se2(1.78 eV) is similar to that of AgGaSe2, thus rendering it highly attractive as a high‐performing nonlinear optical material.

     
    more » « less