Solid-solution semiconductor laser element material and laser element

Abstract: The present invention is to provide a solid solution semiconductor laser element material which can manufacture a laser element which oscillates within an inflated region of wavelength range of 0.4-8 µm, can vary wavelength and can be operable in the vicinity of a room temperature, more particularly to provide a laser element having a lattice matching type double hetero-structure or lattice matching type quantum well structure.

Description: The present invention relates to a solid-solution semiconductor laser element material consisting of a solid-solution semiconductor having the general chemical formulae dislosed in claims 1, 2, 3 and 4, which oscillates within a wide infrared region of wavelength of 0.4-8 µm, and is operable in the vicinity of a room temperature and a laser element with the use of this material. An object of the present invention is to provide a solid solution semiconductor laser element material which can produce a laser element oscillating within an infrared region of wavelength of 0.4-8 µm, varying the wavelength and operating in the vicinity of a room temperature, particularly a laser element having a lattice matching type double hetero-structure or lattice matching type quantum well structure. The structure of a semiconductor laser element is explained by referring to Fig. 1. Figs. 1(A) and 1(B) show a lattice matching type double hetero-structure laser element and a lattice matching type quantum well structure laser element, respectively, wherein a laser beam is emitted from an active layer 2 sandwiched by cladding layers 1, 1 in an arrow direction by flowing a current through an electrode 3. In case of the semiconductor laser element, a laser beam is faint different from the other gas laser, so that it is recently tried to increase luminous efficiency of a laser by a complicated structure dividing an active layer into a barrier layer 4 and a quantum well 5 as shown in Fig. 1(B). As a task required for the above-described semiconductor laser, it is important to increase an operating temperature and to have good junction between a cladding layer and an active layer. Known materials as an active layer and a cladding layer of a semiconductor laser element emitting laser beams with variable wavelength within an infrared region of wavelength of 0.4-8 µm are Hg 1-a Cd a Te, where 0<a≦1, as a II-VI group compound semiconductor, InAs or InSb as a III-V group compound semiconductor and each kind of IV-VI group compound semiconductors. From the view points of high operating temperature and the degree of wavelength variability, the IV-VI group compound semiconductor is noted as the most highly usable material in the above semiconductors, and there have hitherto been known Pb 1-a Cd a S 1-b Se b or Pb 1-a Eu a Te 1-b Se b and the like as a quaternary lead salt solid solution semiconductor. A laser element is formed by making a cladding layer to Pb 1-a Cd a S 1-b Se b or Pb 1-a Eu a Se b Te 1-b by double hetero-structure substantially coincide with the charge carrier and the lattice constant of the cladding layer and the active layer wherein an active layer is formed by one element selected from the group consisting of PbS and Pb 1-a Eu a Se b Te 1-b . Operating temperatures are 200 and 241 K, respectively, but are attained by pulse oscillation, and they have further shortcoming which is lowered by continuous oscillation and these cannot practically be used. In general, in order to increase an operating temperature of the above-described injection-type semiconductor laser, it is desired that a laser element is formed by lattice matching type double hetero-structure or lattice-matching type quantum well structure coincide with each lattice constant of charge carrier and cladding layer and active layer, and that an energy gap of the cladding layer is larger than that of the active layer and its difference is sufficiently large. However, in either one of Pb 1-a Cd a S 1-b Se b or Pb 1-a Eu a Se b Te 1-b , its difference is small, so that the low operating temperature is disadvantageous. In case of forming a laser element by lattice-matching type double hetero-structure or lattice-matching type quantum well structure, it is necessary to form a laser element by jointing materials having a larger energy gap of a cladding layer than that of an active layer, their large difference and substantially equal crystalline structures and lattice constants. In a general chemical formula of Pb 1-a Cd a S 1-b Se b or Pb 1-a Eu a Se b Te 1-b of a quarternary solid solution having a rock salt type crystalline structure, materials having different energy gaps and substantially equal lattice constants are obtained by separately controlling the composition (a) of an element of Cd or Eu and the composition (b) of an element of Se, so that it is possible to form a laser element by joining them. However, in case of actually manufacturing a laser element, a large amount of solid solution of Pb series cannot be expected from the limitation such as manufacturing condition and the like, and a quarternary solid solution is manufactured by a very small amount of solid solution at present. The above-described materials pulse-oscillated at 200 K and 241 K is understood that the compositions (a) of Cd and Eu in the above quarternary solid solution are 0.05 and 0.018, respectively, and a solid solution rate to Pb is small. Therefore, in case of producing them as a beam cladding layer, a difference between energy gaps of a cladding layer and an active layer is very small such as 0.18 (eV) at 300 K at most, 0.094 (eV) at 241 K, and a laser element having a high operating temperature cannot be obtained. The demand for a highly efficient laser element has recently been increased, and it is particularly important to develop a solid solution semiconductor laser element operable in the vicinity of a room temperature. That is, in order to increase an operating temperature of a semiconductor laser, it is an urgent task to obtain a novel solid solution semiconductor having a larger energy gap of a cladding layer than that of an active layer and a sufficiently large difference thereof. The present invention is made to obviate said shortcoming by taking the above points into consideration. The present inventors have made a various study, and discovered that these problems can be solved by solid solving Ca to Pb. The characteristics of the present invention are as follows. An object of the invention is to provide a solid solution semiconductor laser element material having the general chemical formula Pb 1-x Ca x X where, 0<x≦0.5, X is either S or S and Se and/or Te. An another object of the invention is to provide a solid solution semiconductor laser element material having the general chemical formula Pb 1-x (Ca 1-y Y y ) x X where, 0<x≦0.5, 0<y<1, X is either S or S and Se and/or Te, Y is Sr and/or Ba. Still another object of the invention is to provide a solid solution semiconductor laser element material having the general chemical formula Pb 1-x Ca x S 1-z Se z where, 0<x≦0.4, 0≦z≦1. Yet still another object of the invention is to provide a solid solution semiconductor laser element materials having the general chemical formula Pb 1-x (Ca 1-y Sr y ) x S where, 0<x≦0.5, 0≦y<1. Yet still another object of the invention is to provide a laser element wherein said material is used as a cladding layer and/or an active layer. Yet still another object of the invention is to provide a double hetero-structure laser element wherein a material is used as a cladding layer and/or an active layer. Another object of the invention is to provide a quantum well structure laser element wherein said material is used as a cladding layer and/or an active layer. For a better understanding of the invention, reference is made to the accompanying drawings, in which: Fig. 1(a) is a laser element having a lattice matching type double hetero-structure. Fig. 1(B) is a laser element having a lattice matching type quantum well structure. Fig. 2 is a diagram showing the relation of the energy gap between compositions x and z of Pb 1-x Ca x S 1-z Se z at a room temperature. Fig. 3 is a diagram showing the relation of the lattice constant between compositions x and z of Pb 1-x Ca x S 1-z Se z at a room temperature. Fig. 4 is a diagram showing the relation of the energy gap between compositions x and y of Pb 1-x (Ca 1-y Sr y ) x S at a room temperature. Fig. 5 is a diagram showing the relation of the lattice constant between compositions x and y of Pb 1-x (Ca 1-y Sr y ) x S at a room temperature. Present invention is more in detail explained with respect to a method of manufacturing a solid solution semiconductor. Each element is weighed into a desired composition ratio, and sealed in vacuo or a suitable gas atmosphere within a suitable vessel such as a quartz vessel. The vessel is inserted into a suitable oven, such as an electric oven or a suitable heating furnace, for heating, melting and homogenizing, and thereafter, quenching by water is carried out. The thus obtained sample is ground for further homogenization, and again sealed in vacuo or a suitable gas atmosphere such as argon (Ar) within a suitable vessel, such as a quartz vessel, heated at a high temperature for suitable time, and quenching by water, thereby a homogenized solid solution material is obtained. Moreover, the material is formed into a single crystal by a single crystal generating method, such as Bridgeman technique, a vapor phase reaction method and the like. On the other hand, this material is manufactured into a thin film having a suitably shaped thickness by using a thin film manufacturing device, such as MBE method, a HWE method and the like. The present invention is explained in more detail by referring to the drawings. Figs. 2 and 3 show a lattice constant obtained by X-ray powder diffraction method and an energy gap for compositions x, z and compositions x, y with respect to a single crystal of Pb 1-x Ca x S 1-z Se z respectively. Figs. 4 and 5 show a lattice constant obtained by X-ray powder diffraction method and an energy gap for compositions x, z and compositions x, y with respect to a single crystal of Pb 1-x (Ca 1-y Sr y ) x S, respectively. Moreover, the energy gap and the lattice constant are obtained by processing at a room temperature. It is possible to select a combination of materials having a largely different energy gap, their large difference and equal lattice constant. That is, as a combination of a charge carrier in a lattice matching type double hetero-structure laser element or a lattice matching type quantum well structure laser element and materials as a beam cladding layer and an active layer, Fig. 2 shows, for example, that in case of combining Pb 0.95 Ca 0.05 S 0.95 Se 0.05 with PbB, their lattice constants become equal, and a large difference value of 0.24 eV of energy gap can be obtained. Therefore, the present invention can manufacture a lattice matching type double hetero-structure laser element or a lattice matching type quantum well structure laser element which can vary wavelength and can be operable at a temperature in the vicinity of a room temperature. When lattice missmatching occurs at the interface of an active layer and a cladding layer of a laser element, crystal defect such as dislocation is introduced into the active layer, the luminous efficiency is lowered, and the performance of the laser element is deteriorated, so that it is preferable that the lattice constants of the cladding layer and the active layer are almost equal, and matching is good. The reason why the general chemical formulae of the materials according to the present invention are limited to Pb 1-x Ca x X, where 0<x≦0.5, X is either S or S and Se and/or Te, and Pb 1-x (Ca 1-y Y y ) x X, where 0<x≦0.5, 0<y<1, X is either S or S and Se and/or Te, Y is Sr and/or Ba is because if the general chemical formulae are deviated from these composition ranges, the manufacture of a laser element becomes difficult, the operating temperature and luminous efficiency are lowered, and the material becomes unsuitable as laser element material. However, in case of obtaining a solid solution semiconductor from the above stoichiometric composition even there is some deviation, a property as laser element material is not spoiled, but it belongs to category of the present invention. Moreover, Ca as material of the present invention has a remarkable effect of widening a solid solution range with Pb and enlarging energy gap, and further the element selected from the group consisting of Sr, Ba, S, Se and Te have a large effect for controlling a lattice constant of a solid solution semiconductor. [Embodiment] Example 1 With respect to a solid solution semiconductor of Pb 1-x Ca x S 1-z Se z (x=0.02-0.06, z=0.20-0.80), raw materials of granular of Pb, Ca, S and Se of 99.999% purity were weighed to be gross weight 2 g at a desired composition ratio. They were vacuum sealed in a quartz vessel of 8 mm in inner diameter and 40 mm in length under a degree of vacuum of 1×10⁻⁶ Torr, and a synthetic reaction preliminarily proceeded with a weak oxygen-hydrogen flame. Thereafter, the vessel was inserted into an electric oven heated to 1127 K (854°C), maintained for about 10 minutes, thereafter the temperature was raised up to 1393 K (1120°C) at a rate of 50 K/hr, the vessel was heated and maintained at the same temperature for 3 hours to homogeneously melt the contents, and quenched. The thus obtained material was further ground in a mortar, and vacuum sealed into a clean vessel of 8 mm in inner diameter and 50 mm in length and placed at one end. In order to prevent the agitation or unbalance of temperature distribution by an air flow within the oven, this vessel was further vacuum sealed in a quartz vessel to form a double sealing structure. This vessel was placed in a horizontal oven having a temperature gradient of 4 K of a temperature difference between sample temperature of 1223 K and that of a crystal growth portion, it is left for several days for single crystallization, and thereafter quenched to form a solid solution semiconductor laser material. Table 1 shows energy gaps and lattice constants of each of the thus obtained solid solution semiconductors. These values are well matched with energy gaps and lattice constants shown in Figs. 2 and 3. Example 2 With respect to five kinds of a solid solution semiconductor of Pb 1-x (Ca 1-y Sr y ) x S (x=0.10-0.40, y=0.19-0.65), materials of granular of Pb, Ca, Sr and S of 99.999% purity were weighed to be gross weight 2 g at a desired composition ratio. A method of manufacturing a sample is the same as Example 1. Energy gaps and lattice constants of each of the thus obtained solid solution semiconductors are as shown in Table 2. These values are well matched with energy gaps and lattice constants shown in Figs. 4 and 5. Table shows various properties in case of using the typical solid solution semiconductor laser element materials obtained by the present invention as a laser element cladding layer and/or an active layer. Lattice constants of a cladding layer and an active layer are well matched, and a difference between their energy gaps (eV) is large. That is, it is understood that their difference is remarkably improved as compared with a comparative example having the highest value of 0.18 (eV) obtained by the prior art. As apparent from Table 3, Sample Nos. 45 and 49 are the case of using the material of the present invention as an active layer, and Sample Nos. 53 and 59 show the case of using the material of present invention for both the cladding layer and the active layer. Sample No. 70 is not part of the present invention. The other samples show the case of using the material of present invention for a cladding layer. The material according to present invention, depending to the composition, may be preferable for a cladding layer, an active layer and both the cladding layer and the active layer, and it was confirmed that the energy gap and the lattice constant are within a predetermined range. As shown in the above Examples, Tables and drawings, the solid solution semiconductor laser element material according to the present invention is a suitable material for laser element because of a wide solid solution range and a large energy gap. That is, with the use of the present material as a cladding layer, and an active layer is suitably selected from a solid solution semiconductor, such as PbS, PbSe, PbTe, PbS 1-z Se z and the like, having smaller energy gap than that of the cladding layer, its difference being large, substantially the same lattice constants and good lattice matching, or a cladding layer is suitably selected from a solid solution semiconductor, such as In 1-x Ga x As 1-y P y and the like, having a large energy gap, and an active layer is suitably selected from the present material having a smaller energy gap than that of the cladding layer, its difference being large, and good lattice matching, and further both the cladding layer and the active layer are suitably selected from the material according to the present invention having a larger energy gap of a cladding layer than that of an active layer, its large difference being large and good lattice matching, thereby forming a high laser element having high operating temperature and luminous efficiency. Therefore, the laser element of the present invention is suitable for not only a light source of an ultra-high resolution spectroscope within an infrared region of wavelength 0.4-8 µm or quartz glass fiber optical communication used in optical communication at present, but also a light source of optical communication with the use of metal halide polar loss glass fiber having less optical loss in development. The material according to the present invention can easily form a laser element which oscillates within an infrared region of wavelength range of 0.4-8 µm and the material can vary wavelength and it is operable in the vicinity of a room temperature, particularly a lattice matching type double hetero-structure or lattice matching type quantum well structure laser element, so that it is suitable as material of a highly lminous efficient and high-performance laser element, and furthermore, this laser element is suitable as a light source and the like of optical communication system, the ultra-high resolution spectroscope and the other general instruments, and its applicable range of the present material is wide.

Claims: A solid solution semiconductor laser element material having the general chemical formula Pb₁ -x Ca x X wherein 0<x≦0.5; and X is either S or S and Se and/or Te. A solid solution semiconductor laser element material having the general chemical formula Pb 1-x (Ca 1-y Y y ) x X wherein 0<x≦0.5; 0<y<1; X is either S or S and Se and/or Te; and Y is Sr and/or Ba. A solid solution semiconductor laser element material having the general chemical formula Pb 1-x Ca x S 1-z Se z wherein 0<x≦0.4; and 0≦z≦1. A solid solution semiconductor laser element material having the general chemical formula Pb 1-x (Ca 1-y Sr y ) x S wherein 0<x≦0.5; and 0≦y<1. A laser element according to any preceding claim, wherein the material is used as a cladding layer and/or an active layer. A double hetero-structure laser element comprising a cladding layer and/or an active layer formed of the material of any of claims 1-4. A quantum well structure laser element comprising a cladding layer and/or an active layer formed of the material of any of claims 1-4.

Inventors: ABE SEISHI, MASUMOTO KATASHI, MOCHIZUKI KATSUMI, NAKAMURA NAOJI, ABE, SEISHI, MASUMOTO, KATASHI, MOCHIZUKI, KATSUMI, NAKAMURA, NAOJI
Applicants: ELECT & MAGN ALLOYS RES INST, THE FOUNDATION: THE RESEARCH INSTITUTE OF ELECTRIC AND MAGNETIC ALLOYS
Application year: 1992
Main classification: H01S3
IPC codes: H01S5, H01L33