PDF II-VI Compounds: International Series of Monographs in The Science of The Solid State

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You previously purchased this article through ReadCube. Institutional Login. Log in to Wiley Online Library. Purchase Instant Access. View Preview. Currently, only powder-based or thin-film-based ZnS polycrystalline materials are used for this application. Presently only thin-film-based polycrystalline ZnS is used for this application. Currently, powder-based or thin-film-based ZnS polycrystalline materials are usually used for these applications. A ZnS single crystal or a multi-grain ZnS crystal of pure or substantially pure wurtzite structure, which is not available commercially to date, may have a better performance.

Subhananda Chakrabarti

ZnS typically crystallizes in one of two crystal structures: cubic sphalerite, or zinc blende and hexagonal wurtzite. Cleartran is a trademark of Morton International, Inc. Chicago, Ill. In addition to the cubic and hexagonal crystal structures, ZnS has many polytypes. The cubic ZnS also called 3C polytype and the wurtzite-structure ZnS also called 2H polytype crystals are important for practical use. ZnS of different polytypes have different physical properties.

For example, the band gap energy of cubic ZnS is about 2. A ZnS crystal containing more than one polytype, i. Therefore, for many applications, it is favorable to use a ZnS single crystal of a pure or substantially pure polytype. A first method to grow ZnS single crystals is melt-growth. Melt-grown ZnS crystals were found to be of wurtzite structure. However, because the vapor pressure of ZnS at its melting point is very high approximately 3. Further, due to contaminants, mainly from the crucible material contacting the ZnS melt, melt-grown ZnS crystals were found to contain excessive amounts of undesirable impurities and crystalline defects.

A second growth method is a sublimation physical vapor transport PVT.

Crystal Growth - 2nd Edition

A PVT growth is essentially a sublimation and re-condensation process. A source material placed at the high temperature end of a crucible sublimes and the vapor species travel and re-condense onto the other end of the crucible at a lower temperature to form a crystal. But the wurtzite-structure ZnS single crystals produced in this way were impure and of low crystalline perfection. The impurities and defects are believed due to impure ZnS source materials and contaminants from the growth crucibles containers made of a mullite tube or a fused silica tube.

PVT growth technique. But, the growth rate at these low temperatures is quite low, typically less than 0. The cubic ZnS crystals produced in this way are doped by I iodine and therefore have an n-type conduction. Semiconductor devices built on such n-type cubic ZnS single crystals are disclosed in U. However, the growth rate in iodine transport technique for ZnS is extremely slow less than 0. Cleartran ZnS and Multi-spectral ZnS materials still have some level of absorption and scattering likely due to residual structural defects and impurity clusters.

However, because of the high mechanical strength of ZnS, a ZnS with a low bulk absorption coefficient less than 0. On the other hand, the CVD process for producing ZnS has a slow deposition rate usually in the range of 0.

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CVD-ZnS crystals or Cleartran ZnS crystals are polycrystalline materials that cannot be used for applications such as semiconductor devices, laser mediums, substrate materials, etc. For optical applications, particularly IR applications including optics for FLIR and high power CO 2 lasers, there exists a need of ZnS single crystals or multi-grain ZnS crystals with a better performance and a less cost to produce. There also exists a need for ZnS single crystals or multi-grain ZnS crystals of pure or substantially pure hexagonal structure for many non-optical applications.

There is also a potential use of ZnS crystals of substantially pure wurtzite structure in many applications that have not yet been identified. The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects and advantages of the invention will be apparent from the description and drawings, and from the claims. Disclosed herein are ZnS single crystals or multi-grain ZnS crystals that possess superior physical properties and are suitable for many applications, as well as methods to produce the ZnS single crystals or multi-grain ZnS crystals.

In addition, a zinc sulfide ZnS single crystals or multi-grain ZnS crystal of pure or substantially pure hexagonal wurtzite structure with a low bulk absorption coefficient less than 0. One embodiment of this invention is a ZnS single crystal or a multi-grain ZnS crystal of pure or substantially pure wurtzite structure with a high chemical purity at least These wurtzite-structure ZnS single crystals and multi-grain crystals are suitable for fabricating optical components including, but not limited to, IR, forward looking IR FLIR and high power CO 2 laser components, such as windows, lenses, prisms, beam splitters, filters, wave plates, operated in the visible and IR spectrum range of 0.

Another embodiment of this invention is a ZnS single crystal or a multi-grain ZnS crystal of pure or substantially pure wurtzite structure that is intentionally doped with one or more impurities including, but not limited to, the transition metal elements and rare-earth elements and such doped ZnS single crystals and multi-grain crystals are suitable for fabricating photoluminescence devices, such as scintillation detectors for detection or imaging of radiations of UV light, X-rays, gamma-rays, and neutrons.

Another embodiment in this invention is a ZnS single crystal or a multi-grain ZnS crystal of pure or substantially pure wurtzite structure that is intentionally doped with one or more impurities selected from the transition metal elements and rare-earth elements and such doped ZnS single crystals and multi-grain crystals are suitable for fabricating cathode luminescence devices, such as cathode ray tubes CRTs , CRT-type television sets, field emission displays, or other devices for detection, displaying or imaging of electron beams also known as cathode rays.

Yet another embodiment of this invention is a ZnS single crystal or a multi-grain ZnS crystal of pure or substantially pure wurtzite structure that is intentionally doped with one impurity activator or more impurities, and such doped ZnS single crystals and multi-grain crystals are suitable for fabricating electro-luminescence EL devices including but not limited to devices emitting visible lights e. Still another embodiment of this invention is a ZnS single crystal or a multi-grain ZnS crystal or a multi-grain ZnS crystal of pure or substantially pure wurtzite structure that is unintentionally doped that is doped with residual impurities from the ZnS source material or intentionally doped with one or more electronically-active impurities so that the ZnS single crystals and multi-grain crystals are either electrically insulating, or semi-insulating, or conducting i.

Yet another embodiment of this invention is a ZnS single crystal of pure or substantially pure wurtzite structure that is intentionally doped with one or more impurities selected from the transition metal elements e. Another embodiment of this invention is a sublimation physical vapor transport method, unseeded or otherwise seeded with a ZnS crystal seed, to produce all the aforementioned ZnS single crystals or multi-grain ZnS crystals of pure or substantially pure hexagonal wurtzite structure, undoped or doped, using a high purity ZnS material as source material and a high purity crucible.

While still another embodiment of this invention is a chemical-assisted vapor transport method, unseeded or otherwise seeded with a ZnS crystal seed, to produce all the aforementioned ZnS single crystals or multi-grain ZnS crystals of pure or substantially pure hexagonal wurtzite structure, undoped or doped, utilizing a gas such as H 2 , H 2 S, or I 2 , and a high purity ZnS material as source material, and a high-purity, non-reactive crucible. Yet another embodiment of this invention is a chemical vapor deposition method, unseeded or otherwise seeded with a ZnS crystal seed, to produce all the aforementioned ZnS single crystals or multi-grain ZnS crystals of pure or substantially pure hexagonal wurtzite structure, undoped or doped, utilizing a Zn vapor and a H 2 S gas as source materials and a carrier gas or gas mixture selected from H 2 , Ar, N 2 and He, and in a high-purity, non-reactive crucible.

Like reference numbers and designations in the various drawings indicated like elements. A first method to produce ZnS single crystal and multi-grain ZnS crystal of pure or substantially pure wurtzite structure is a physical vapor transport method. Besides the intrinsic vacancies in some compounds by nature, the formation of solid solutions with a solvent having a smaller cation-to-anion ratio as compared to the matrix is expected to create vacancies because the crystal structure needs to be stabilized in that of the matrix compound. In this work, In 2 Te 3 and Ga 2 Te 3 i , compounds with a smaller cation-to-anion ratio as compared to the CuGaTe 2 matrix, are chosen as molecular solvents to form solid solutions.

This work demonstrates a useful strategy for enhancing thermoelectric performance by vacancy creation in solid solutions. The article was received on 18 Jul , accepted on 02 Sep and first published on 02 Sep If you are not the author of this article and you wish to reproduce material from it in a third party non-RSC publication you must formally request permission using Copyright Clearance Center. Go to our Instructions for using Copyright Clearance Center page for details.

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