CN101194053A - Method for producing gaxin1-xn(0<=x<=1=1) crystal, gaxin1-xn(0<=x<=1=1) crystalline substrate, method for producing gan crystal, gan crystalline substrate, and product - Google Patents

Abstract

In the conventional GaN crystal production method using HVPE process, there is a possibility of improving the crystallizing property of a GaN crystal by conducting the method at a temperature higher than 1100 DEG C. However, the method has a problem that a quartz reaction tube (1) could be melt when the heating with heaters (5) and (6) is conducted at a temperature higher than 1100 DEG C. Thus, provided is a method for production of a GaxIn1-xN (0=x=1) crystal (12) comprising the step of reacting a raw gas comprising at least one of a halogenated gallium gas and a halogenated indium gas and an ammonium gas in a quartz reaction tube (1) to make grow the GaxIn1-xN (0=x=1) crystal (12) on the surface of a substrate (7), wherein the quartz reaction tube (1) is externally heated during making grow the the GaxIn1-xN (0=x=1) crystal (12) and the substrate (7) is also heated separately.

Description

Make Ga xIn 1-xN(0≤x≤1) crystalline method, Ga xIn 1-xN(0≤x≤1) crystalline substrate, manufacturing GaN crystalline method, GaN crystalline substrate and product

Technical field

The present invention relates to a kind of Ga that is used for making _xIn _1-xN (0≤x≤1) crystalline method, Ga _xIn _1-xN (0≤x≤1) crystalline substrate and comprise Ga _xIn _1-xThe product of N (0≤x≤1) crystalline substrate.More specifically, the present invention relates to a kind ofly can make Ga with good crystallinity _xIn _1-xN (0≤x≤1) crystalline Ga _xIn _1-xN (0≤x≤1) crystal manufacture method, the Ga that obtains by this manufacture method _xIn _1-xN (0≤x≤1) crystalline substrate and comprise Ga _xIn _1-xThe product of N (0≤x≤1) crystalline substrate.

The invention still further relates to a kind of product that is used for making GaN crystalline method, GaN crystalline substrate and comprises the GaN crystalline substrate.More specifically, the present invention relates to a kind ofly can to make GaN crystalline GaN crystal manufacture method, utilize GaN crystalline substrate that this manufacture method obtains and the product that comprises this GaN crystalline substrate with good crystallinity.

Background technology

At Ga _xIn _1-xIn N (0≤x≤1) crystal, GaN (gan) crystal has the band gap of 3.4eV and high heat conductivity, and therefore as be used for semiconducter device for example short wavelength's optics device and power electronic device material and cause concern.

As making this GaN crystalline method, conventional HVPE (hydride gas-phase epitaxy) method of using.Fig. 2 illustrates to be used for utilizing HVPE to make the synoptic diagram of structure of an example of the producing apparatus of GaN crystalline ordinary method.This producing apparatus comprises crystal reaction tube 1, be used for gas is introduced the inlet pipe 2 and 3 and be connected to the exhaust gas treatment device 8 of crystal reaction tube 1 of crystal reaction tube 1.

In crystal reaction tube 1 inside, place gallium source boat 4 and basic substrate 7 that it contains gallium (Ga).Then, by inlet pipe 2 and 3 with supporting gas such as nitrogen (N ₂) gas, argon (Ar) gas or hydrogen (H ₂) gas introduces crystal reaction tube 1, and by well heater 5 and 6 gallium source boat 4 and basic substrate 7 are heated to about 1000 ℃.Then, in crystal reaction tube 1, introduce ammonia (NH by inlet pipe 2 ₃) gas, and pass through inlet pipe 3 and in crystal reaction tube 1, introduce hydrogenchloride (HCl) gas.As a result, at first, gallium and hydrogen chloride gas precursor reactant form gallium chloride (GaCl) gas.Then, gallium chloride gas and ammonia gas react make growing GaN crystal 12 on the surface of basic substrate 7.After the growth of having finished GaN crystal 12, stop well heater 5 and 6 heating, with about gallium source boat 4, GaN crystal 12 and basic substrate 7 cool to room temperature., will have the in its surface basic substrate 7 taking-up crystal reaction tubes 1 of Grown GaN crystal 12, and remove basic substrate 7 by grinding then and obtain GaN crystal 12 thereafter.

Patent documentation 1: Japanese Patent Application Laid-Open No.2001-181097

Summary of the invention

The problem to be solved in the present invention

By utilizing HVPE to make this ordinary method of GaN crystalline, seem to seem to improve GaN crystalline degree of crystallinity by making the GaN crystal in the temperature that is higher than 1100 ℃.Yet in fact, when being heated to above 1100 ℃ temperature by well heater 5 and 6, crystal reaction tube 1 will melt, and therefore can not crystal reaction tube 1 be heated to above 1100 ℃ temperature by utilizing well heater 5 and 6, makes the GaN crystal.

Therefore, the purpose of this invention is to provide and a kind ofly can make Ga with good crystallinity _xIn _1-xN (0≤x≤1) crystalline Ga _xIn _1-xN (0≤x≤1) crystal manufacture method, the Ga that obtains by this manufacture method _xIn _1-xN (0≤x≤1) crystalline substrate and comprise this Ga _xIn _1-xThe product of N (0≤x≤1) crystalline substrate.

Another object of the present invention provides a kind ofly can make the GaN crystalline GaN crystal manufacture method with good crystallinity, utilizes GaN crystalline substrate that this manufacture method obtains and the product that comprises this GaN crystalline substrate.

The mode that addresses these problems

The present invention relates to a kind of manufacturing Ga _xIn _1-xN (0≤x≤1) crystalline method, this method be by in crystal reaction tube, the reaction of at least a material gas by comprising ammonia and gallium halide gas and indium halide gas, and Ga grows on the surface of basic substrate _xIn _1-xN (0≤x≤1) crystal is made Ga _xIn _1-xN (0≤x≤1) crystal is wherein at Ga _xIn _1-xDuring N (0≤x≤1) crystal growth, crystal reaction tube is heated separately by indirect heating and basic substrate.

At Ga according to the present invention _xIn _1-xIn N (0≤x≤1) the crystal manufacture method, basic substrate can heat separately by the well heater that is provided at basic substrate back side.

In addition, at Ga according to the present invention _xIn _1-xIn N (0≤x≤1) the crystal manufacture method, basic substrate can be by utilizing the high-frequency induction heating system to heat separately.

In addition, at Ga according to the present invention _xIn _1-xIn N (0≤x≤1) the crystal manufacture method, gallium halide gas can form by the reaction between gallium and the halogen gas.

In addition, at Ga according to the present invention _xIn _1-xIn N (0≤x≤1) the crystal manufacture method, indium halide gas can form by the reaction between indium and the halogen gas.

In addition, at Ga according to the present invention _xIn _1-xIn N (0≤x≤1) the crystal manufacture method, hydrogen chloride gas can be used as halogen gas.

In addition, at Ga according to the present invention _xIn _1-xIn N (0≤x≤1) the crystal manufacture method, basic substrate is preferably by any formation the in silicon, sapphire, silicon carbide, gan and the aluminium nitride.

In addition, at Ga according to the present invention _xIn _1-xIn N (0≤x≤1) the crystal manufacture method, the Ga of growth _xIn _1-xN (0≤x≤1) crystal can have 1 * 10 ¹⁸Cm ^-3Or lower impurity concentration.

In addition, at Ga according to the present invention _xIn _1-xIn N (0≤x≤1) the crystal manufacture method, the Ga of growth _xIn _1-xN (0≤x≤1) crystal can comprise 1 * 10 ¹⁷Cm ^-3Or greater concn select at least a in the group that free carbon, magnesium, iron, beryllium, zinc, vanadium and antimony forms as impurity, and can have 1 * 10 ⁴Ω cm or higher resistivity.

In addition, at Ga according to the present invention _xIn _1-xIn N (0≤x≤1) the crystal manufacture method, can make Ga _xIn _1-xN (0≤x≤1) crystal growth is for being doped with n type impurity.

In addition, at Ga according to the present invention _xIn _1-xIn N (0≤x≤1) the crystal manufacture method, the Ga of growth _xIn _1-xN (0≤x≤1) crystal can comprise 1 * 10 ¹⁷Cm ^-3Or greater concn be selected from least a in the group of forming by oxygen, silicon, sulphur, germanium, selenium and tellurium as n-type impurity, and can have 1 Ω cm or lower resistivity.

In addition, at Ga according to the present invention _xIn _1-xIn N (0≤x≤1) the crystal manufacture method, the Ga of growth _xIn _1-xN (0≤x≤1) crystal can comprise and selects at least a as impurity in the group that free carbon, oxygen and silicon forms, and can have and be not less than 1 * 10 ¹⁷Cm ^-3But be not higher than 1 * 10 ¹⁹Cm ^-3N _Eff, n _EffRepresent by following formula: n _Eff=n _o+ n _Si-n _c(n here _cBe carbon content, n _oBe oxygen level, and n _SiBe silicone content), and can have 0.1 Ω cm or lower resistivity.

In addition, at Ga according to the present invention _xIn _1-xIn N (0≤x≤1) the crystal manufacture method, the Ga of growth _xIn _1-xN (0≤x≤1) crystal preferably has and is not less than 5 * 10 ¹⁵Cm ^-3But be lower than 1 * 10 ¹⁷Cm ^-3Carbon content n _c, be not less than 1 * 10 ¹⁷Cm ^-3But be not higher than 2 * 10 ¹⁸Cm ^-3Oxygen level n _o, be not less than 1 * 10 ¹⁷Cm ^-3But be not higher than 2 * 10 ¹⁸Cm ^-3Silicone content n _SiAnd be not less than 0.01 Ω cm but be not higher than the resistivity of 0.1 Ω cm.

In addition, at Ga according to the present invention _xIn _1-xIn N (0≤x≤1) the crystal manufacture method, the Ga of growth _xIn _1-xN (0≤x≤1) crystal can have 200 μ m or higher thickness.

In addition, at Ga according to the present invention _xIn _1-xIn N (0≤x≤1) the crystal manufacture method, at growth Ga _xIn _1-xDuring N (0≤x≤1) crystal, basic substrate temperature preferably is higher than 1100 ℃ but be not higher than 1400 ℃.

In addition, at Ga according to the present invention _xIn _1-xIn N (0≤x≤1) the crystal manufacture method, at growth Ga _xIn _1-xDuring N (0≤x≤1) crystal, basic substrate temperature preferably is higher than 1150 ℃ and still is not higher than 1400 ℃.

In addition, at Ga according to the present invention _xIn _1-xIn N (0≤x≤1) the crystal manufacture method, at growth Ga _xIn _1-xDuring N (0≤x≤1) crystal, the temperature of the crystal reaction tube of outer heating preferably be not less than 800 ℃ but be not higher than 1100 ℃, and basic substrate temperature preferably be higher than 1100 ℃ but be not higher than 1400 ℃.

In addition, at Ga according to the present invention _xIn _1-xIn N (0≤x≤1) the crystal manufacture method, at growth Ga _xIn _1-xDuring N (0≤x≤1) crystal, the temperature of the crystal reaction tube of outer heating preferably be not less than 800 ℃ but be not higher than 950 ℃, and basic substrate temperature preferably be higher than 950 ℃ but be not higher than 1400 ℃.

The invention still further relates to a kind of manufacturing Ga _xIn _1-xN (0≤x≤1) crystalline method, this method be by in crystal reaction tube, the reaction of at least a material gas by comprising ammonia and gallium halide gas and indium halide gas, and Ga grows on the surface of basic substrate _xIn _1-xN (0≤x≤1) crystal is made Ga _xIn _1-xN (0≤x≤1) crystal is wherein at Ga _xIn _1-xDuring N (0≤x≤1) crystal growth, basic substrate temperature is higher than 1100 ℃ and still is not higher than 1400 ℃.

The invention still further relates to a kind of manufacturing Ga _xIn _1-xN (0≤x≤1) crystalline method, this method is by in crystal reaction tube, and by comprising the reaction of at least a material gas in ammonia and gallium halide gas and the indium halide gas, Ga grows on the surface of basic substrate _xIn _1-xN (0≤x≤1) crystal is made Ga _xIn _1-xN (0≤x≤1) crystal is wherein at Ga _xIn _1-xDuring N (0≤x≤1) crystal growth, basic substrate temperature is higher than 1150 ℃ and still is not higher than 1400 ℃.

The invention still further relates to by by above-mentioned manufacturing Ga _xIn _1-xThe Ga of any acquisition of N (0≤x≤1) crystal method _xIn _1-xThe Ga that N (0≤x≤1) crystal is formed _xIn _1-xN (0≤x≤1) crystalline substrate.

The invention still further relates to and comprise this Ga _xIn _1-xThe product of N (0≤x≤1) crystalline substrate.The invention still further relates to a kind of manufacturing GaN crystalline method, this method is made the GaN crystal by in crystal reaction tube by growing GaN crystal on the surface that is reflected at basic substrate of material gas, and wherein material gas comprises gallium halide gas and ammonia; Wherein during the GaN crystal growth, crystal reaction tube is heated separately by indirect heating and basic substrate.

In GaN crystal manufacture method according to the present invention, basic substrate can heat separately by the well heater that is arranged on basic substrate back side.

In addition, in GaN crystal manufacture method according to the present invention, basic substrate can be by utilizing the high-frequency induction heating system to heat separately.

In addition, in GaN crystal manufacture method according to the present invention, gallium halide gas can form by the reaction between gallium and the halogen gas.

In addition, in GaN crystal manufacture method according to the present invention, hydrogen chloride gas can be used as halogen gas.

In addition, in GaN crystal manufacture method according to the present invention, the Grown GaN crystal can have 1 * 10 ¹⁸Cm ^-3Or lower impurity concentration.

In addition, in GaN crystal manufacture method according to the present invention, the Grown GaN crystal can comprise 1 * 10 ¹⁷Cm ^-3Or greater concn select at least a in the group that free carbon, magnesium, iron, beryllium, zinc, vanadium and antimony forms as impurity, and have 1 * 10 ⁴Ω cm or higher resistivity.

In addition, in GaN crystal manufacture method according to the present invention, can make the GaN crystal growth for being doped with n type impurity.

In addition, in GaN crystal manufacture method according to the present invention, the Grown GaN crystal can comprise 1 * 10 ¹⁷Cm ^-3Or greater concn be selected from least a in the group of forming by oxygen, silicon, sulphur, germanium, selenium and tellurium as n type impurity, and can have 1 Ω cm or lower resistivity.

In addition, in GaN crystal manufacture method according to the present invention, the Grown GaN crystal can comprise and selects at least a as impurity in the group that free carbon, oxygen and silicon forms, and can have and be not less than 1 * 10 ¹⁷Cm ^-3But be not higher than 1 * 10 ¹⁹Cm ^-3N _Eff, this n _EffRepresent by following formula: n _Eff=n _o+ n _Si-n _c(n here _cBe carbon content, n _oBe oxygen level, and n _SiBe silicone content), and can have the resistivity that is not higher than 0.1 Ω cm.

In addition, in GaN crystal manufacture method according to the present invention, the Grown GaN crystal preferably has and is not less than 5 * 10 ¹⁵Cm ^-3But be lower than 1 * 10 ¹⁷Cm ^-3Carbon content n _c, be not less than 1 * 10 ¹⁷Cm ^-3But be not higher than 2 * 10 ¹⁸Cm ^-3Oxygen level n _o, be not less than 1 * 10 ¹⁷Cm ^-3But be not higher than 2 * 10 ¹⁸Cm ^-3Silicone content n _SiAnd be not less than 0.01 Ω cm but be not higher than the resistivity of 0.1 Ω cm.

In addition, in GaN crystal manufacture method according to the present invention, the Grown GaN crystal can have 200 μ m or higher thickness.

In addition, in GaN crystal manufacture method according to the present invention, basic substrate is preferably formed by gan.

In addition, in GaN crystal manufacture method according to the present invention, the surface of basic substrate preferably has 10 μ m or littler arithmetical mean degree of roughness Ra.

In addition, in GaN crystal manufacture method according to the present invention, during the growing GaN crystal, basic substrate temperature preferably is higher than 1100 ℃ and still is not higher than 1300 ℃.

In addition, in GaN crystal manufacture method according to the present invention, during the growing GaN crystal, basic substrate temperature preferably is higher than 1150 ℃ and still is not higher than 1250 ℃.

In addition, in GaN crystal manufacture method according to the present invention, during the growing GaN crystal, the temperature of the crystal reaction tube of outer heating preferably be not less than 800 ℃ but be not higher than 1100 ℃, and basic substrate temperature preferably be higher than 1100 ℃ but be not higher than 1300 ℃.

In addition, in GaN crystal manufacture method according to the present invention, during the growing GaN crystal, the temperature of the crystal reaction tube of outer heating preferably be not less than 800 ℃ but be not higher than 950 ℃, and basic substrate temperature preferably be higher than 950 ℃ but be not higher than 1300 ℃.

In addition, in GaN crystal manufacture method according to the present invention, during the growing GaN crystal, the temperature of the crystal reaction tube of outer heating preferably be not less than 800 ℃ but be not higher than 1100 ℃, and basic substrate temperature preferably be higher than 1150 ℃ but be not higher than 1250 ℃.

In addition, in GaN crystal manufacture method according to the present invention, during the growing GaN crystal, the temperature of the crystal reaction tube of outer heating preferably be not less than 800 ℃ but be not higher than 950 ℃, and basic substrate temperature preferably be higher than 1150 ℃ but be not higher than 1250 ℃.

The invention still further relates to a kind of manufacturing GaN crystalline method, this method is made the GaN crystal by in crystal reaction tube by growing GaN crystal on the surface that is reflected at basic substrate of material gas, and wherein material gas comprises gallium halide gas and ammonia; Wherein during the GaN crystal growth, basic substrate temperature is higher than 1100 ℃ and still is not higher than 1300 ℃.

The invention still further relates to a kind of manufacturing GaN crystalline method, this method is made the GaN crystal by in crystal reaction tube by growing GaN crystal on the surface that is reflected at basic substrate of material gas, and wherein material gas comprises gallium halide gas and ammonia; Wherein during the GaN crystal growth, basic substrate temperature is higher than 1150 ℃ and still is not higher than 1250 ℃.

The invention still further relates to a kind of GaN crystalline substrate of forming by the GaN crystal that obtains by any above-mentioned manufacturing GaN crystalline method.

The invention still further relates to a kind of product that comprises this GaN crystalline substrate.

The invention effect

According to the present invention, can provide a kind of and can make Ga with good crystallinity _xIn _1-xN (0≤x≤1) crystalline Ga _xIn _1-xN (0≤x≤1) crystal manufacture method, the Ga that obtains by this manufacture method _xIn _1-xN (0≤x≤1) crystalline substrate and comprise this Ga _xIn _1-xThe product of N (0≤x≤1) crystalline substrate.

According to the present invention, can also provide a kind of and can make GaN crystalline GaN crystal manufacture method with good crystallinity, utilize this manufacture method GaN crystalline substrate that obtains and the product that comprises this GaN crystalline substrate.

Description of drawings

Fig. 1 illustrates the synoptic diagram that is used for according to the structure of a preferred embodiment of the producing apparatus of manufacturing of the present invention GaN crystalline method.

Fig. 2 is the synoptic diagram of structure that an example of the producing apparatus that is used to make GaN crystalline ordinary method is shown.

Fig. 3 illustrates the synoptic diagram that is used for according to the structure of another preferred embodiment of the producing apparatus of manufacturing of the present invention GaN crystalline method.

The reference marker explanation

1: crystal reaction tube; 2,3: inlet pipe; 4: gallium source boat; 5,6,11: well heater; 7: basic substrate; 8: exhaust gas treatment device; 9: power supply; 10: lead; The 12:GaN crystal; 13: radio-frequency coil; 14: the carbon back up pad

Embodiment

Hereinafter, will an example of the present invention be described with reference to make GaN crystalline situation by growing GaN crystal on the surface of the basic substrate that constitutes by the GaN crystal.Should be noted that in figure of the present invention identical reference number is represented identical part or corresponding part.

Fig. 1 illustrates the synoptic diagram that is used to make according to the structure of a preferred embodiment of the producing apparatus of GaN crystalline method of the present invention.Producing apparatus shown in Fig. 1 comprises crystal reaction tube 1 as reactor, be used for gas is incorporated into inlet pipe 2 and 3 in the crystal reaction tube 1, is arranged on crystal reaction tube 1 external heated device 5 and 6 and the exhaust gas treatment device 8 that is connected to crystal reaction tube 1.

In crystal reaction tube 1 inside of producing apparatus with said structure, the gallium source boat 4 that provides basic substrate 7 and Qi Nei to comprise gallium; And on the rear side of basic substrate 7, provide well heater 11.In this, it is noted that well heater 11 is connected to power supply 9 by the lead of being made by for example molybdenum (Mo) 10.

At first, at least a supporting gas that will be selected from the group of being made up of for example nitrogen, argon gas and hydrogen by inlet pipe 2 and 3 is introduced crystal reaction tube 1, simultaneously, heating is arranged on crystal reaction tube 1 external heated device 5 and 6 and be arranged on well heater 11 on basic substrate 7 rear side.By adding hot heater 5 and 6, gallium source boat 4 and basic substrate 7 have been heated.By adding hot heater 11, further improved the temperature of basic substrate 7.

In this, preferably be not less than 800 ℃ by the temperature that is arranged on crystal reaction tube 1 external heated device 5 and 6 crystal reaction tubes that heat and still be not higher than 1100 ℃, more preferably be not less than 800 ℃ and still be not higher than 950 ℃.If the temperature by well heater 5 and 6 crystal reaction tubes that heat is lower than 800 ℃, will worry that so gallium source boat 4 is not fully heated, therefore and suppressed reaction between halogen gas and the gallium (this will be described later) during the GaN crystal growth, caused reducing the gallium halide of making growing GaN crystal needs thus, and produced a large amount of byproducts except that GaN or gallium drip droplet.If the temperature by well heater 5 and 6 crystal reaction tubes that heat is higher than 1100 ℃, crystal reaction tube will melt.Be higher than in the temperature of crystal reaction tubes under 950 ℃ the situation by well heater 5 and 6 heating, mass productivity is often poor, because may quicken the degeneration of crystal reaction tube 1 by well heater 5 and 6 heating, and shortened life-span of crystal reaction tube 1, so crystal reaction tube 1 can not be reused.On the other hand, by will be set at by the temperature of crystal reaction tubes of well heater 5 and 6 heating be not less than 800 ℃ but be not higher than 950 ℃, can prevent effectively during the GaN crystal growth that non-impurity of having a mind to from dispersing, suppress this non-impurity of having a mind to thus and sneak in the GaN crystal.In addition, by will be set at by the temperature of crystal reaction tubes of well heater 5 and 6 heating be not less than 800 ℃ but be not higher than 950 ℃, can suppress the consumption of material gas, and the efficient that has therefore improved the GaN crystal production (just, the ratio of Grown GaN crystalline amount and the amount of the material that provides), because, for example reach the reaction that prevents to produce material gas before the basic substrate 7 in material gas, arrive crystal reaction tube 1 with the product adhesion of avoiding gained.

By the temperature of the basic substrate 7 that is arranged on well heater 11 heating on basic substrate 7 rear side preferably be higher than 950 ℃ but be not higher than 1400 ℃, more preferably be higher than 1100 ℃ but be not higher than 1400 ℃, even more preferably be higher than 1150 ℃ but be not higher than 1400 ℃.If the temperature of basic substrate 7 is higher than 1400 ℃, will worry during the GaN crystal growth (this will be described later) that GaN crystalline rate of decomposition is significantly higher than GaN crystalline productivity, cause having reduced GaN crystalline growth rate thus.When the temperature higher (just, for example, temperature is elevated to 950 ℃, 1100 ℃ and 1150 ℃ in order) of basic substrate 7, Grown GaN crystalline degree of crystallinity is tending towards higher.

Particularly, under the situation of growing on the surface of the basic substrate 7 that the GaN crystal is being made by gan, during the GaN crystal growth, the temperature of base substrate 7 preferably is higher than 950 ℃ and still is not higher than 1300 ℃, more preferably be higher than 1100 ℃ but be not higher than 1300 ℃, even more preferably be higher than 1150 ℃ but be not higher than 1250 ℃.This is because the inventor has been found that, when the temperature of the basic substrate of making by gan 7 higher (just, for example, temperature is elevated to 950 ℃, 1100 ℃ and 1150 ℃ in order) time, Grown GaN crystalline degree of crystallinity is higher, and in addition, during polishing, seldom in the lip-deep GaN crystal wafer that is grown in the basic substrate 7 that is heated to higher temperature, produce and break, improved the yield rate of making the GaN crystalline substrate thus.Though the seldom generation of breaking that know-why that can not be definite can think to have fewer purpose focal point of stress at comparatively high temps Grown GaN crystal.In addition, under the situation of growing on the surface of the basic substrate 7 that the GaN crystal is being made by gan, because above-mentioned reason, the temperature of basic substrate 7 preferably is higher than 1150 ℃, but when the temperature of basic substrate 7 is high more, the easy more generation of thermolysis of the basic substrate of forming by the GaN crystal 7.If the temperature of basic substrate 7 surpasses 1300 ℃, the decomposition of basic substrate 7 just is tending towards significantly, with induced damage resistive base substrate 7.The temperature of basic substrate 7 be higher than 1250 ℃ but be not higher than under 1300 ℃ the situation, the decomposition of basic substrate 7 is not remarkable, but is to a certain degree carrying out.Therefore, in this case, when making the GaN crystal growth long-time, because basic substrate trend is compromised, so can not give birth to long GaN crystal.

In the present invention, by will be set at by the temperature of crystal reaction tubes of well heater 5 and 6 heating for example be not less than 800 ℃ but be not higher than 950 ℃ temperature, and by the temperature with basic substrate 7 be set at for example be higher than 1100 ℃ but be not higher than 1400 ℃ or be higher than 1150 ℃ but be not higher than 1400 ℃ temperature, can heat gallium source boat 4, prevent crystal reaction tube 1 simultaneously owing to the heating of well heater 5 and 6 is melted, and the temperature of basic substrate 7 can be set at the temperature higher than the temperature of fusion of crystal reaction tube 1.

Particularly, under the situation of growing on the surface of the basic substrate 7 that the GaN crystal is being made by gan, during the GaN crystal growth, by will be set at by the temperature of crystal reaction tubes of well heater 5 and 6 heating preferably be not less than 800 ℃ but be not higher than 1100 ℃, more preferably be not less than 800 ℃ and still be not higher than 950 ℃ temperature, and by the temperature with basic substrate 7 be set at preferably be higher than 950 ℃ but be not higher than 1300 ℃, more preferably be higher than 1100 ℃ and still be not higher than 1300 ℃, even more preferably be higher than 1150 ℃ but be not higher than 1250 ℃ temperature, that is to say, be set at than the high temperature of temperature by temperature by well heater 5 and 6 crystal reaction tubes that heat with basic substrate 7, can heat gallium source boat 4 and prevent that simultaneously crystal reaction tube 1 is owing to the heating of well heater 5 and 6 is melted, the temperature of basic substrate 7 can be set at the temperature higher than the temperature of fusion of crystal reaction tube 1, Grown GaN crystalline degree of crystallinity can be improved, and the yield rate of GaN crystalline substrate product can be improved.Should be noted that by well heater 5 and the temperature of crystal reaction tubes of 6 heating and the temperature of basic substrate 7 to remain unchanged substantially, finish up to the GaN crystal growth.

Then, by inlet pipe 2 with ammonia in supporting gas is introduced crystal reaction tube 1, simultaneously, by inlet pipe 3 with halogen gas for example hydrogen chloride gas in supporting gas is introduced crystal reaction tube 1.

Here, preferred, during the GaN crystal growth, the dividing potential drop of the dividing potential drop of halogen gas and ammonia is respectively to be not less than 1 * 10 in the crystal reaction tube 1 ^-2Atm still is not higher than 0.2atm and is not less than 5 * 10 ^-2Atm still is not higher than 0.9atm.This trends towards allowing the GaN crystal with 10 μ m/h or higher speed growth.

More preferably, during the GaN crystal growth, the dividing potential drop of the dividing potential drop of halogen gas and ammonia is respectively to be not less than 2 * 10 in the crystal reaction tube 1 ^-2Atm but be not higher than 0.1atm and be not less than 0.2atm but be not higher than 0.7atm.This trends towards allowing the GaN crystal with 30 μ m/h or higher speed growth, and the polycrystal GaN crystal of not growing.

At the halogen gas of introducing to crystal reaction tube 1 by inlet pipe 3 is under the situation of hydrogen chloride gas, arrives the hydrogen chloride gas and the gallium reaction that is contained in the gallium source boat 4 of gallium source boat 4, forms gallium halide gas, just gallium chloride (GaCl) gas.

Then, the material gas that comprises gallium halide gas and ammonia arrives the surface of the basic substrate 7 of heating, the reaction of the material gas by comprising gallium halide gas and ammonia, growing GaN crystal 12 on the surface of basic substrate 7.

After the growth of having finished GaN crystal 12, the temperature of GaN crystal 12 is lowered to about room temperature, and will have the basic substrate 7 taking-up crystal reaction tubes 1 that are grown in its lip-deep GaN crystal 12.

By for example grind, remove basic substrate 7 to obtain GaN crystal 12 thereafter.

In the present invention, as mentioned above, since basic substrate 7 except by be arranged on crystal reaction tube 1 external heated device 5 and 6 the heating, also heat separately by the well heater 11 that is arranged on crystal reaction tube 1 inside, so can make the temperature of basic substrate 7 be higher than temperature by the crystal reaction tube 1 of well heater 5 and 6 indirect heating, quickened to comprise in the crystal reaction tube 1 reaction of the material gas of gallium halide gas and ammonia thus, and do not have fused quartz reaction tubes 1, and improved the degree of crystallinity of GaN crystal 12 thus.

Except by adding separately the hot radical substrate 7, can make the temperature of the crystal reaction tube 1 of indirect heating be lower than the temperature that degeneration takes place crystal reaction tube 1, and crystal reaction tube 1 is reused, improved mass productivity thus.

GaN crystal 12 to such acquisition carries out mirror polish, removes the damaged layer that is caused by polishing then, makes the GaN crystalline substrate.Alternatively, before mirror polish, GaN crystal 12 can be cut into the sheet with pre-determined thickness.In this case, also remove the damaged layer that causes by polishing, make the GaN crystalline substrate.In this, the cut direction of GaN crystal 12 is not specifically limited, and can be parallel to or favours at any angle the surface of the basic substrate 7 that does not also remove.

Note, be described above with reference to the manufacturing of GaN crystalline, but according to the present invention, comprise by halogen gas (as hydrogen chloride gas) with in the replacement that is provided with by utilization and to hold the material gas of the indium halide gas (for example indium chloride gas) that the reaction between the indium that holds in the indium source boat of gallium source boat of gallium forms within it, also can make the InN crystal.Certainly,, except GaN crystal and InN crystal, comprise the material gas of gallium halide gas and indium halide gas, also can make Ga by utilization according to the present invention _xIn _1-xN (0≤x≤1) crystal.

In the present invention, basic substrate can utilize the heating of high-frequency induction heating system.In this case, for example, as shown in Figure 3, basic substrate 7 is placed on the carbon back up pad 14, radio-frequency coil 13 is wrapped on the part of corresponding basic substrate 7 positions of crystal reaction tube 1 periphery at least, and by apply high-frequency current induction heating carbon back up pad 14 to radio-frequency coil 13, to add hot radical substrate 7 by the heat that produces.

The basic substrate that will use in the present invention is preferably by any the making in silicon, sapphire, silicon carbide (SiC), gan (GaN) and the aluminium nitride (AlN).Particularly, made by gan under the situation of basic substrate, it shows and Ga _xIn _1-xN (0≤x≤1) is the lattice match of excellence especially, therefore can make to have the more Ga of high-crystallinity _xIn _1-xN (0≤x≤1) crystal.

Under the situation of growing on the surface that makes the GaN crystal at basic substrate, basic substrate is especially preferably made by gan.In this case, because basic substrate and will on the surface of basic substrate, have identical lattice parameter by the Grown GaN crystal,, prevented in the Grown GaN crystal generation warpage thus effectively or broken so the Grown GaN crystal has good degree of crystallinity.

In addition, under the situation of growing on the surface of the basic substrate that the GaN crystal is being made by gan, the arithmetical mean degree of roughness Ra of basic substrate surface preferably is not more than 10 μ m, more preferably no more than 1 μ m.Be set at by arithmetical mean degree of roughness Ra and be not more than 10 μ m, during the GaN crystal growth, can prevent the generation of breaking that causes by basic substrate effectively basic substrate surface.Be set at by arithmetical mean degree of roughness Ra and be not more than 1 μ m, can further strengthen this effect basic substrate surface.In this, be noted that in the present invention that term " arithmetical mean degree of roughness Ra " refers to the arithmetic degree of roughness Ra of definition in JIS B0601 2001.

In the present invention, from improving Ga _xIn _1-xThe angle of N (0≤x≤1) crystal purity is considered, the Ga of growth _xIn _1-xN (0≤x≤1) crystalline impurity concentration preferably is not more than 1 * 10 ¹⁸Cm ^-3By utilizing above-mentioned HVPE method, can reduce from the sneaking into of the impurity of background, allow the highly purified Ga of growth thus _xIn _1-xN (0≤x≤1) crystal.

Though be described hereinbefore with reference to make the GaN crystalline substrate by the GaN crystal, much less, according to the present invention, also can be enough and the identical mode of GaN crystalline situation, by Ga _xIn _1-xN (0≤x≤1) crystal is made Ga _xIn _1-xN (0≤x≤1) crystalline substrate.

In addition, be described in the above, but according to the present invention, Ga also can grow on the middle layer that is formed at some type on the basic substrate surface with reference to the situation that the GaN crystal is grown on the surface of basic substrate _xIn _1-xN (0≤x≤1) crystal.

In addition, according to the present invention, also can grow to comprise is not less than 1 * 10 ¹⁷Cm ^-3Concentration select at least a of group that free carbon, magnesium, iron, beryllium, zinc, vanadium and antimony forms as impurity, and have and be not less than 1 * 10 ¹⁴The Ga of the resistivity of Ω cm _xIn _1-xN (0≤x≤1) crystal.As mentioned above because by utilizing the HVPE method can reduce from the sneaking into of the impurity of background (background), so easily wittingly controlled doping advance Ga _xIn _1-xThe amount of the impurity in N (0≤x≤1) crystal makes to obtain to have easily to be not less than 1 * 10 ¹⁴The insulation Ga of the resistivity of Ω cm _xIn _1-xN (0≤x≤1) crystal.In this, be included in Ga at two or more impurity _xIn _1-xUnder the situation in N (0≤x≤1) crystal, the total concn of these impurity should be not less than 1 * 10 ¹⁷Cm ^-3It is noted that in the present invention term " resistivity " means Ga in the time of 25 ℃ _xIn _1-xN (0≤x≤1) crystalline resistivity.

In addition, according to the present invention, also can grow to comprise is not less than 1 * 10 ¹⁷Cm ^-3Concentration be selected from least a in the group of forming by oxygen, silicon, sulphur, germanium, selenium and tellurium as n type impurity and Ga with the resistivity that is not higher than 1 Ω cm _xIn _1-xN (0≤x≤1) crystal.As mentioned above because by utilizing the HVPE method can reduce from the sneaking into of the impurity of background, so easily wittingly controlled doping advance Ga _xIn _1-xThe amount of the impurity in N (0≤x≤1) crystal makes to obtain the conduction Ga that resistivity is not higher than 1 Ω cm easily _xIn _1-xN (0≤x≤1) crystal.In this, be included in Ga at two or more impurity _xIn _1-xUnder the situation in N (0≤x≤1) crystal, the total concn of these impurity should be not less than 1 * 10 ¹⁷Cm ^-3

In addition, according to the present invention, also can grow comprises at least a Ga as impurity that selects in the group that free carbon, oxygen and silicon forms _xIn _1-xN (0≤x≤1) crystal; This crystal has and is not less than 1 * 10 ¹⁷Cm ^-3But be not higher than 1 * 10 ¹⁹Cm ^-3N _Eff, this n _EffBy following formulate: n _Eff=n _o+ n _Si-n _c(n here _cBe the content of carbon, n _oBe the content of oxygen, and n _SiBe the content of silicon); And this crystal has the resistivity that is not more than 0.1 Ω cm.In this, at n _EffBe lower than 1 * 10 ¹⁷Cm ^-3Situation under, resistivity trends towards increasing.On the other hand, at n _EffBe higher than 1 * 10 ¹⁹Cm ^-3Situation under, Ga _xIn _1-xN (0≤x≤1) crystalline degree of crystallinity trends towards reducing.

In addition, according to the present invention, also can grow comprises carbon, oxygen and the silicon Ga as impurity _xIn _1-xN (0≤x≤1) crystal; This crystal has and is not less than 5 * 10 ¹⁵Cm ^-3But be lower than 1 * 10 ¹⁷Cm ^-3Carbon content n _c, be not less than 1 * 10 ¹⁷Cm ^-3But be not higher than 2 * 10 ¹⁸Cm ^-3Oxygen level n _oBe not less than 1 * 10 ¹⁷Cm ^-3But be not higher than 2 * 10 ¹⁸Cm ^-3Silicone content n _SiThis crystal has and is not less than 1 * 10 ¹⁷Cm ^-3But be not higher than 1 * 10 ¹⁹Cm ^-3N _Eff, this n _EffBy following formulate: n _Eff=n _o+ n _Si-n _cAnd this crystal has the resistivity that is not less than 0.01 Ω cm but is not higher than 0.1 Ω cm.In this, at oxygen level n _oOr silicone content n _SiBe higher than 2 * 10 ¹⁸Cm ^-3Situation under, at Ga _xIn _1-xBe easy to generate in N (0≤x≤1) crystal and break.

In the present invention, making Ga _xIn _1-xUnder the situation of N (0≤x≤1) crystalline substrate, preferably make Ga _xIn _1-xN (0≤x≤1) crystal has 200 μ m or bigger thickness, and under the situation of making the GaN crystalline substrate, preferred growth GaN crystal is to have 200 μ m or bigger thickness.

According to the present invention by Ga _xIn _1-xThe Ga that N (0≤x≤1) crystal constitutes _xIn _1-xN (0≤x≤1) crystal structure substrate, can be with the substrate that acts on as the product of semiconducter device, SAW (surface acoustic wave) device, transverter (transducer), vibrator, MEMS parts and piezo-activator, wherein for example optics is (for example for semiconducter device, photodiode, laser diode), electron device (for example, rectifier, bipolar transistor, field-effect transistor, HEMT) and semiconductor transducer (for example, temperature sensor, pressure transmitter, radiation sensor, visible-UV photodetector).These products can pass through at Ga according to the present invention _xIn _1-xLaminate semiconductor layer on the surface of N (0≤x≤1) crystalline substrate and/or metal level is made.

Example

(example 1)

By having stood mirror polish and having removed basic substrate 7 that gan (GaN) crystal of the damaged layer that is caused by polishing constitutes and the gallium source boat 4 that accommodates gallium in it, be placed in the crystal reaction tube 1 shown in Fig. 1.The diameter and the thickness of base substrate 7 are respectively 2 inches and 400 μ m.The surface of base substrate 7 has the surface direction of (001).

Then, by inlet pipe 2 and 3 high-purity hydrogen is introduced crystal reaction tube 1 as supporting gas, simultaneously, temperature by well heater 5 and 6 crystal reaction tubes that heat is increased to 950 ℃, and add hot radical substrate 7 separately by the well heater 11 that is arranged on basic substrate 7 rear side, the temperature that makes basic substrate 7 is 1200 ℃.

Subsequently, the temperature that remains on 950 ℃ and basic substrate 7 in the temperature of crystal reaction tubes by well heater 5 and 6 heating remains in 1200 ℃, by inlet pipe 2 ammonia is introduced crystal reaction tube 1 together with hydrogen, and hydrogen chloride gas is introduced crystal reaction tube 1 together with hydrogen by inlet pipe 3.Hydrogen chloride gas forms gallium chloride gas with the reaction of the gallium that comprises in gallium source boat 4, and the reaction of the material gas by comprising gallium chloride gas and ammonia then, growing GaN crystal 12 on the surface of basic substrate 7.Should be noted that at GaN crystal 12 growing periods the dividing potential drop of hydrogen chloride gas and the dividing potential drop of ammonia in the control crystal reaction tube 1 make with 30 μ m/h or higher speed growing GaN crystal 12, and the polycrystalline of not growing.More specifically, during growing GaN crystal 12, the dividing potential drop of the hydrogen chloride gas in the crystal reaction tube 1 is controlled at 2 * 10 ^-2In the scope of atm to 0.1atm, and the dividing potential drop of ammonia in the crystal reaction tube 1 is controlled in the scope of 0.2atm to 0.7atm.

After the thick GaN crystal 12 of the 400 μ m that on the surface of basic substrate 7, grown with this growth velocity, the temperature of GaN crystal 12 is reduced to room temperature.Then, growth on the surface there is the basic substrate 7 of GaN crystal 12 take out crystal reaction tube 1.Remove basic substrate 7 by grinding, thus obtained GaN crystal 12 is carried out mirror polish, and remove the damaged layer that causes by polishing, make the GaN crystalline substrate.

Analyze the degree of crystallinity of GaN crystalline substrate by XRD (X-ray diffraction), the result is 40 seconds in the whole width for half maximum of the rocking curve of (004) face of this GaN crystalline substrate.By this result, find that the GaN crystalline substrate has good degree of crystallinity.

In addition, observe the interior zone of 10 squares of mu m ranges of GaN crystalline substrate by AFM (atomic force microscope), the result finds that this GaN crystalline substrate has good RMS (rootmean-square) surface roughness that is not more than 50nm.

In addition, analyzed the GaN crystalline substrate with SIMS (secondary ion mass spectrometry), the result finds that the GaN crystalline substrate comprises about 2 * 10 ¹⁷Cm ^-3The oxygen of concentration is as major impurity, and the total concn that is included in all impurity in the GaN crystalline substrate is not more than 1 * 10 ¹⁸Cm ^-3

(example 2)

With with the identical mode of example 1 and under identical condition, make GaN crystal 12 growths shown in Fig. 1 have the thickness of 5mm, then, remove the basic substrate of making by gan 7 fully by grinding.Then, cutting GaN crystal 12 on the direction on basic substrate 7 surfaces of the GaN crystal 12 of having grown on be parallel to is to make the GaN crystal wafer that four thickness are 500 μ m.Each all carries out mirror polish these four GaN crystal wafers, and has removed the damaged layer that is caused by polishing afterwards.In this way, four GaN crystalline substrate have been made.

By XRD analysis the degree of crystallinity of these four GaN crystalline substrate, the result, the whole width of half maximum of (004) face rocking curve of each GaN crystalline substrate is not more than 40 seconds.By this result, all as can be seen GaN crystalline substrate have good degree of crystallinity.

In addition, observed zone in each 10 squares of mu m ranges of these four GaN crystalline substrate by AFM, the result finds that each GaN crystalline substrate all has the good rms surface degree of roughness that is not more than 50nm.

And, each of these four GaN crystalline substrate of usefulness sims analysis, the result finds that each GaN crystalline substrate comprises about 2 * 10 ¹⁷Cm ^-3The oxygen of concentration is as major impurity, and all total concns that are included in the impurity in each GaN crystalline substrate are not more than 1 * 10 ¹⁸Cm ^-3

(example 3)

Except hydrogen chloride gas and ammonia also with dichlorosilane (SiH ₂Cl ₂) introduce crystal reaction tube 1, except this point, use the mode identical and under identical condition with example 1, make to comprise silicon and on the surface of the basic substrate 7 shown in Fig. 1, grow as the GaN crystal 12 of n type impurity.Then, remove basic substrate 7 to make the siliceous GaN crystal 12 of 400 μ m thickness.

Then, to carrying out mirror polish, and remove the damaged layer that causes by polishing, make the GaN crystalline substrate by remove the GaN crystal 12 that basic substrate 7 obtains by grinding.

By the degree of crystallinity of this GaN crystalline substrate of XRD analysis, the result, the whole width of half maximum of (004) face rocking curve of GaN crystalline substrate is 40 seconds.By this result, can find that this GaN crystalline substrate has good degree of crystallinity.

In addition, with this GaN crystalline substrate of sims analysis, the result finds that the GaN crystalline substrate comprises about 1 * 10 ¹⁸Cm ^-3The silicon of concentration is as major impurity.

As mentioned above, in example 3, use dichlorosilane, even but can think and use silicon tetrachloride (SiCl as the silicon source ₄) replace dichlorosilane also can obtain the result identical with example 3.In addition, even can think that dichlorosilane and silicon tetrachloride use together, also can obtain the result identical with example 3.In addition, also can obtain the result identical even can think to use except that dichlorosilane and silicon source the silicon tetrachloride with example 3.

(example 4)

Will be by through mirror polish and removed basic substrate 7 that gan (GaN) crystal of the damaged layer that is caused by polishing constitutes and be placed on the carbon back up pad 14 in the crystal reaction tube 1 that is arranged on shown in Fig. 3.The diameter and the thickness of base substrate 7 are respectively 2 inches and 400 μ m.The surface of base substrate 7 has the surface direction of (001).In addition, the gallium source boat 4 that holds gallium in it is placed in the crystal reaction tube 1.

Then, by inlet pipe 2 and 3 high-purity hydrogen is introduced crystal reaction tube 1 as supporting gas, simultaneously, to be increased to 950 ℃ by the temperature of well heater 5 and 6 crystal reaction tubes that heat, and provide high-frequency current by radio-frequency coil to the peripheral portion of the crystal reaction tube that is wrapped in corresponding basic substrate 7 positions, come high-frequency induction heating carbon back up pad 14, so that the temperature of basic substrate 7 is 1200 ℃.

Subsequently, the temperature that remains on 950 ℃ and basic substrate 7 in the temperature of crystal reaction tubes by well heater 5 and 6 heating remains in 1200 ℃, introduces ammonia by inlet pipe 2 with hydrogen, and introduces hydrogen chloride gas by inlet pipe 3 with hydrogen.Hydrogen chloride gas forms gallium chloride gas with the gallium reaction that is contained in the gallium source boat 4, the reaction of the material gas by comprising gallium chloride gas and ammonia afterwards, growing GaN crystal 12 on the surface of basic substrate 7.Should be noted that at GaN crystal 12 growing periods the dividing potential drop of hydrogen chloride gas and the dividing potential drop of ammonia in the control crystal reaction tube 1 make GaN crystal 12 grow with the speed that is not less than 30 μ m/h, and the polycrystal of not growing.More specifically, during growing GaN crystal 12, the dividing potential drop of hydrogen chloride gas in the crystal reaction tube 1 is controlled at 2 * 10 ^-2In the scope of atm to 0.1atm, and the dividing potential drop of ammonia gas in the crystal reaction tube 1 is controlled in the scope of 0.2atm to 0.7atm.

On the surface of basic substrate 7, grown after the thick GaN crystal 12 of 400 μ m, the temperature of GaN crystal 12 has been reduced to room temperature with this growth velocity.Then, will have the basic substrate 7 that is grown in its lip-deep GaN crystal 12 and take out crystal reaction tube 1.Remove basic substrate 7 by grinding, thus obtained GaN crystal 12 is carried out mirror polish, and remove the damaged layer that causes by polishing, to make the GaN crystalline substrate.

On this GaN crystalline substrate, do not observe and break.By the degree of crystallinity of this GaN crystalline substrate of XRD analysis, the result, the whole width of half maximum of (004) face rocking curve of this GaN crystalline substrate is 40 seconds.By this result, can find that this GaN crystalline substrate has good degree of crystallinity.

In addition, with sims analysis GaN crystalline substrate, the result finds that the GaN crystalline substrate comprises about 2 * 10 ¹⁷Cm ^-3The oxygen of concentration is as major impurity, and all total concns that are included in the impurity in the GaN crystalline substrate are not more than 1 * 10 ¹⁸Cm ^-3

(comparative example 1)

Use the producing apparatus shown in Fig. 2, and be 1050 ℃, and not heating separately of basic substrate 7, in addition, use the mode growing GaN crystal identical with example 1 by the temperature of the crystal reaction tubes 1 of well heater shown in Fig. 25 and 6 heating.

Then, remove basic substrate 7, thus obtained GaN crystal 12 is carried out mirror polish, and remove the damaged layer that causes by polishing, to make the GaN crystalline substrate by grinding.

By the degree of crystallinity of this GaN crystalline substrate of XRD analysis, the result, the whole width of half maximum of (004) face rocking curve of GaN crystalline substrate is 100 seconds, this compares very big with example 1 to 4.By this result, the GaN crystal of finding comparative example 1 is very poor with respect to degree of crystallinity the GaN crystal of example 1 to 4.

By this result, find, except the indirect heating crystal reaction tube,, can improve GaN crystalline degree of crystallinity by basic substrate is heated to higher temperature.

(example 5)

With the mode identical with example 1, make 12 growths of GaN crystal have the thickness of 400 μ m, the temperature by the crystal reaction tubes of well heater shown in Fig. 15 and 6 heating remains on 850 ℃ simultaneously, and the temperature of the basic substrate 7 that is made of the GaN crystal remains on 1200 ℃.At GaN crystal 12 growing periods, the dividing potential drop of the gas of control composition material gas, the growth velocity that makes GaN crystal 12 is 200 μ m/h.

Under identical partial pressure, make GaN crystal 12 to grow with identical as mentioned above mode, the temperature by well heater 5 and 6 crystal reaction tubes that heat remains on 1050 ℃ simultaneously, and the temperature of basic substrate 7 remains on 1200 ℃.As a result, the growth velocity of GaN crystal 12 becomes 50 μ m/h.

By the result of example 5, find that the manufacturing efficient of GaN crystal 12 is when the temperature by the crystal reaction tubes of well heater 5 and 6 heating is 1050 ℃ four times high when the temperature by the crystal reaction tubes of well heater 5 and 6 heating is 850 ℃.

(example 6)

With the mode identical and under identical condition with example 1, make 12 growths of GaN crystal have the thickness of 10mm, the temperature of the basic substrate 7 that is made of the GaN crystal remains on 1200 ℃ simultaneously.Then, cutting Grown GaN crystal 12 also carries out mirror polish, with make ten each all have the GaN crystalline substrate of 400 μ m thickness.In these ten GaN crystalline substrate, do not find to break.

In this, should be noted that in temperature to remain on 1050 ℃, in the mode identical and under identical condition with example 1 except basic substrate 7, make under the situation of GaN crystal 12 growths, observed in three GaN crystalline substrate in ten GaN crystalline substrate and broken.

(example 7)

As the basic substrate 7 shown in Fig. 1, prepared ten and be not less than 0.1 μ m but but the basic substrate that the GaN crystal that is not more than the arithmetical mean surface roughness Ra of 0.5 μ m constitutes and ten are not less than 15 μ m the basic substrate that the GaN crystal that is not more than the arithmetical mean surface roughness Ra of 20 μ m constitutes by having by having.Then, use the mode identical and under identical condition, the GaN crystal 12 of 10mm thickness is grown on the surface of each basic substrate 7 with example 1.

Make GaN crystal 12 be grown in ten by having under the lip-deep situation that is not less than 0.1 μ m but is not more than in the basic substrate 7 that the GaN crystal of the arithmetical mean surface roughness Ra of 0.5 μ m constitutes each, be grown in these ten basic substrates 7 each on GaN crystal 12 in do not observe and break.

On the other hand, be not less than 15 μ m but be not more than under each the lip-deep situation in the basic substrate 7 that the GaN crystal of the arithmetical mean surface roughness Ra of 20 μ m constitutes by having making GaN crystal 12 be grown in ten, be grown in these ten three basic substrates 7 in the basic substrate 7 each on GaN crystal 12 in observed and broken.

(example 8)

Except hydrogen chloride gas and ammonia, also used by the reaction between iron and the hydrogen chloride gas and formed iron(ic) chloride gas, in addition, use the mode identical and under identical condition, make to comprise iron and be grown on the surface of the basic substrate 7 shown in Fig. 1 as the GaN crystal 12 of impurity with example 1.Then, remove basic substrate 7, to make the iron content GaN crystal 12 of 400 μ m thickness.

Then, remove basic substrate 7, thus obtained GaN crystal 12 is carried out mirror polish, and remove the damaged layer that causes by polishing, to make the GaN crystalline substrate by grinding.

With this GaN crystalline substrate of sims analysis, the result, discovery is approximately 1 * 10 as the concentration of the iron that impurity comprises ¹⁸Cm ^-3In the time of 25 ℃, the resistivity of this GaN crystalline substrate is approximately 1 * 10 ¹⁷Ω cm.

(example 9)

Except hydrogen chloride gas and ammonia, also using silicon tetrachloride gas, use the mode identical and under identical condition with example 1, make to comprise silicon and be grown on the surface of the basic substrate 7 shown in Fig. 1 as the GaN crystal 12 of impurity.Then, remove basic substrate 7, to make the siliceous GaN crystal 12 of 400 μ m thickness.

Then, carry out mirror polish to remove the GaN crystal 12 that basic substrate 7 obtains by grinding, and remove the damaged layer that causes by polishing, to make the GaN crystalline substrate.

With this GaN crystalline substrate of sims analysis, the result finds that the GaN crystalline substrate comprises about 1 * 10 ¹⁸Cm ^-3The silicon of concentration is as major impurity, and comprises and be respectively about 5 * 10 ¹⁷Cm ^-3With about 2 * 10 ¹⁷Cm ^-3The carbon of concentration and oxygen are as non-impurity of having a mind to.In the time of 25 ℃, the resistivity of this GaN crystalline substrate is approximately 0.01 Ω cm.

Embodiment disclosed herein and example will think it all is illustrative in all respects, rather than restrictive.Therefore scope of the present invention is defined by the following claims, rather than is limited by description above, and the institute in the scope of the equivalence of the border of claim and restriction or this border and restriction changes, and should be comprised by claim.

The industry practicality

The present invention can be applied to Ga_xIn _1-xManufacturing, the Ga of N (0≤x≤1) crystal_xIn _1-xThe manufacturing of N (0≤x≤1) crystalline substrate and comprise Ga_xIn _1-xThe product of N (0≤x≤1) crystalline substrate Manufacturing. Specifically, the present invention can advantageous applications to manufacturing, the GaN crystallization lining of GaN crystal The manufacturing at the end and comprise the manufacturing of the product of GaN crystalline substrate.

Claims (47)

1. make Ga for one kind _xIn _1-xThe method of N (0≤x≤1) crystal (12), this method be by in crystal reaction tube (1), and by comprising the reaction of the material gas of at least a and ammonia in gallium halide gas and the indium halide gas, Ga grows on the surface of basic substrate (7) _xIn _1-xN (0≤x≤1) crystal (12) is made Ga _xIn _1-xN (0≤x≤1) crystal is wherein at described Ga _xIn _1-xThe growing period of N (0≤x≤1) crystal (12) externally heats described crystal reaction tube (1) and heats described basic substrate (7) individually.

2. according to the manufacturing Ga of claim 1 _xIn _1-xThe method of N (0≤x≤1) crystal (12), wherein said basic substrate (7) is by being arranged on well heater (11) heating separately on described basic substrate (7) rear side.

3. according to the manufacturing Ga of claim 1 _xIn _1-xThe method of N (0≤x≤1) crystal (12), wherein said basic substrate (7) is by utilizing the high-frequency induction heating system to heat separately.

4. according to the manufacturing Ga of claim 1 _xIn _1-xThe method of N (0≤x≤1) crystal (12), wherein said gallium halide gas forms by the reaction between gallium and the halogen gas.

5. according to the manufacturing Ga of claim 4 _xIn _1-xThe method of N (0≤x≤1) crystal (12), wherein said halogen gas is a hydrogen chloride gas.

6. according to the manufacturing Ga of claim 1 _xIn _1-xThe method of N (0≤x≤1) crystal (12), wherein said indium halide gas forms by the reaction between indium and the halogen gas.

7. according to the manufacturing Ga of claim 6 _xIn _1-xThe method of N (0≤x≤1) crystal (12), wherein said halogen gas is a hydrogen chloride gas.

8. according to the manufacturing Ga of claim 1 _xIn _1-xThe method of N (0≤x≤1) crystal (12), wherein said basic substrate (7) is by any the making in silicon, sapphire, silicon carbide, gan and the aluminium nitride.

9. according to the manufacturing Ga of claim 1 _xIn _1-xThe method of N (0≤x≤1) crystal (12), wherein Sheng Chang Ga _xIn _1-xN (0≤x≤1) crystal (12) has 1 * 10 ¹⁸Cm ^-3Or lower impurity concentration.

10. according to the manufacturing Ga of claim 1 _xIn _1-xThe method of N (0≤x≤1) crystal (12), wherein Sheng Chang Ga _xIn _1-xN (0≤x≤1) crystal (12) comprises 1 * 10 ¹⁷Cm ^-3Or greater concn select at least a in the group that free carbon, magnesium, iron, beryllium, zinc, vanadium and antimony forms as impurity, and have 1 * 10 ⁴Ω cm or higher resistivity.

11. manufacturing Ga according to claim 1 _xIn _1-xThe method of N (0≤x≤1) crystal (12) wherein makes Ga _xIn _1-xN (0≤x≤1) crystal (12) is grown to and is doped with n type impurity.

12. manufacturing Ga according to claim 11 _xIn _1-xThe method of N (0≤x≤1) crystal (12), wherein Sheng Chang Ga _xIn _1-xN (0≤x≤1) crystal comprises 1 * 10 ¹⁷Cm ^-3Or greater concn be selected from least a in the group of forming by oxygen, silicon, sulphur, germanium, selenium and tellurium as described n type impurity, and have 1 Ω cm or lower resistivity.

13. manufacturing Ga according to claim 1 _xIn _1-xThe method of N (0≤x≤1) crystal (12), wherein Sheng Chang Ga _xIn _1-xN (0≤x≤1) crystal comprises and selects at least a as impurity in the group that free carbon, oxygen and silicon forms, and has and be not less than 1 * 10 ¹⁷Cm ^-3But be not higher than 1 * 10 ¹⁹Cm ^-3N _Eff, this n _EffBy following formulate: n _Eff=n _o+ n _Si-n _c(n here _cBe carbon content, n _oBe oxygen level, and n _SiBe silicone content), and have 0.1 Ω cm or lower resistivity.

14. manufacturing Ga according to claim 13 _xIn _1-xThe method of N (0≤x≤1) crystal (12), wherein Sheng Chang Ga _xIn _1-xN (0≤x≤1) crystal (12) has and is not less than 5 * 10 ¹⁵Cm ^-3But be lower than 1 * 10 ¹⁷Cm ^-3Described carbon content n _c, be not less than 1 * 10 ¹⁷Cm ^-3But be not higher than 2 * 10 ¹⁸Cm ^-3Described oxygen level n _o, be not less than 1 * 10 ¹⁷Cm ^-3But be not higher than 2 * 10 ¹⁸Cm ^-3Described silicone content n _SiBe not less than 0.01 Ω cm but be not higher than the resistivity of 0.1 Ω cm.

15. manufacturing Ga according to claim 1 _xIn _1-xThe method of N (0≤x≤1) crystal (12), wherein Sheng Chang Ga _xIn _1-xN (0≤x≤1) crystal (12) has 200 μ m or higher thickness.

16. manufacturing Ga according to claim 1 _xIn _1-xThe method of N (0≤x≤1) crystal (12) is wherein at the described Ga of growth _xIn _1-xDuring N (0≤x≤1) crystal (12), the temperature of described basic substrate (7) is higher than 1100 ℃ and still is not higher than 1400 ℃.

17. manufacturing Ga according to claim 1 _xIn _1-xThe method of N (0≤x≤1) crystal (12) is wherein at the described Ga of growth _xIn _1-xDuring N (0≤x≤1) crystal (12), the temperature of described basic substrate (7) is higher than 1150 ℃ and still is not higher than 1400 ℃.

18. manufacturing Ga according to claim 1 _xIn _1-xThe method of N (0≤x≤1) crystal (12) is wherein at the described Ga of growth _xIn _1-xDuring N (0≤x≤1) crystal (12), externally the temperature of Jia Re described crystal reaction tube (1) be not less than 800 ℃ but be not higher than 1100 ℃, and the temperature of described basic substrate (7) be higher than 1100 ℃ but be not higher than 1400 ℃.

19. manufacturing Ga according to claim 1 _xIn _1-xThe method of N (0≤x≤1) crystal (12) is wherein at the described Ga of growth _xIn _1-xDuring N (0≤x≤1) crystal (12), externally the temperature of Jia Re described crystal reaction tube (1) be not less than 800 ℃ but be not higher than 950 ℃, and the temperature of described basic substrate (7) be higher than 950 ℃ but be not higher than 1400 ℃.

20. make Ga for one kind _xIn _1-xThe method of N (0≤x≤1) crystal (12), this method be by in crystal reaction tube (1), and by comprising the reaction of the material gas of at least a and ammonia in gallium halide gas and the indium halide gas, Ga grows on the surface of basic substrate (7) _xIn _1-xN (0≤x≤1) crystal (12) is made Ga _xIn _1-xN (0≤x≤1) crystal is wherein at described Ga _xIn _1-xThe growing period of N (0≤x≤1) crystal (12), the temperature of described basic substrate (7) are higher than 1100 ℃ and still are not higher than 1400 ℃.

21. make Ga for one kind _xIn _1-xThe method of N (0≤x≤1) crystal (12), this method be by in crystal reaction tube (1), and by comprising the reaction of the material gas of at least a and ammonia in gallium halide gas and the indium halide gas, Ga grows on the surface of basic substrate (7) _xIn _1-xN (0≤x≤1) crystal (12) is made Ga _xIn _1-xN (0≤x≤1) crystal is wherein at described Ga _xIn _1-xThe growing period of N (0≤x≤1) crystal (12), the temperature of described basic substrate (7) are higher than 1150 ℃ and still are not higher than 1400 ℃.

22. Ga _xIn _1-xN (0≤x≤1) crystalline substrate comprises by the manufacturing Ga according to claim 1 _xIn _1-xThe Ga that the method for N (0≤x≤1) crystal (12) obtains _xIn _1-xN (0≤x≤1) crystal (12).

23. a product, it comprises the Ga according to claim 22 _xIn _1-xN (0≤x≤1) crystalline substrate.

24. method of making GaN crystal (12), this method is by in crystal reaction tube (1), the reaction of the material gas by comprising gallium halide gas and ammonia, growing GaN crystal (12) is made the GaN crystal on the surface of basic substrate (7), wherein, externally heat described crystal reaction tube (1) and heat described basic substrate (7) individually at the growing period of described GaN crystal (12).

25. according to the method for the manufacturing GaN crystal (12) of claim 24, wherein said basic substrate (7) heats separately by the well heater that is arranged on described basic substrate (7) rear side.

26. according to the method for the manufacturing GaN crystal (12) of claim 24, wherein said basic substrate (7) is by utilizing the high-frequency induction heating system to heat separately.

27. according to the method for the manufacturing GaN crystal (12) of claim 24, wherein said gallium halide gas forms by the reaction between gallium and the halogen gas.

28. according to the method for the manufacturing GaN crystal (12) of claim 27, wherein said halogen gas is a hydrogen chloride gas.

29. according to the method for the manufacturing GaN crystal (12) of claim 24, wherein Grown GaN crystal (12) has 1 * 10 ¹⁸Cm ^-3Or lower impurity concentration.

30. according to the method for the manufacturing GaN crystal (12) of claim 24, wherein Grown GaN crystal (12) comprises 1 * 10 ¹⁷Cm ^-3Or greater concn select at least a in the group that free carbon, magnesium, iron, beryllium, zinc, vanadium and antimony forms as impurity, and have 1 * 10 ⁴Ω cm or higher resistivity.

31. the method according to the manufacturing GaN crystal (12) of claim 24 wherein makes GaN crystal (12) be grown to and is doped with n type impurity.

32. according to the method for the manufacturing GaN crystal (12) of claim 31, wherein Grown GaN crystal (12) comprises 1 * 10 ¹⁷Cm ^-3Or greater concn be selected from least a in the group of forming by oxygen, silicon, sulphur, germanium, selenium and tellurium as described n type impurity, and have 1 Ω cm or lower resistivity.

33. according to the method for the manufacturing GaN crystal (12) of claim 24, wherein Grown GaN crystal (12) comprises and selects at least a as impurity in the group that free carbon, oxygen and silicon forms, and has and be not less than 1 * 10 ¹⁷Cm ^-3But be not higher than 1 * 10 ¹⁹Cm ^-3N _Eff, this n _EffBy following formulate: n _Eff=n _o+ n _Si-n _c(n here _cBe carbon content, n _oBe oxygen level, and n _SiBe silicone content), and have the resistivity that is not higher than 0.1 Ω cm.

34. according to the method for the manufacturing GaN crystal (12) of claim 33, wherein Grown GaN crystal (12) has and is not less than 5 * 10 ¹⁵Cm ^-3But be lower than 1 * 10 ¹⁷Cm ^-3Described carbon content n _c, be not less than 1 * 10 ¹⁷Cm ^-3But be not higher than 2 * 10 ¹⁸Cm ^-3Described oxygen level n _o, be not less than 1 * 10 ¹⁷Cm ^-3But be not higher than 2 * 10 ¹⁸Cm ^-3Described silicone content n _SiAnd be not less than 0.01 Ω cm but be not higher than the resistivity of 0.1 Ω cm.

35. according to the method for the manufacturing GaN crystal (12) of claim 24, wherein Grown GaN crystal (12) has the thickness that is not less than 200 μ m.

36. according to the method for the manufacturing GaN crystal (12) of claim 24, wherein said basic substrate (7) is made by gan.

37. according to the method for the manufacturing GaN crystal (12) of claim 24, the surface of wherein said basic substrate (7) has 10 μ m or littler arithmetical mean degree of roughness Ra.

38. according to the method for the manufacturing GaN crystal (12) of claim 24, wherein during the described GaN crystal of growth (12), the temperature of described basic substrate (7) be higher than 1100 ℃ but be not higher than 1300 ℃.

39. according to the method for the manufacturing GaN crystal (12) of claim 24, wherein during the described GaN crystal of growth (12), the temperature of described basic substrate (7) be higher than 1150 ℃ but be not higher than 1250 ℃.

40. method according to the manufacturing GaN crystal (12) of claim 24, wherein during the described GaN crystal of growth (12), externally the temperature of Jia Re described crystal reaction tube (1) be not less than 800 ℃ but be not higher than 1100 ℃, and the temperature of described basic substrate (7) be higher than 1100 ℃ but be not higher than 1300 ℃.

41. method according to the manufacturing GaN crystal (12) of claim 24, wherein during the described GaN crystal of growth (12), externally the temperature of Jia Re described crystal reaction tube (1) be not less than 800 ℃ but be not higher than 950 ℃, and the temperature of described basic substrate (7) be higher than 950 ℃ but be not higher than 1300 ℃.

42. method according to the manufacturing GaN crystal (12) of claim 24, wherein during the described GaN crystal of growth (12), externally the temperature of Jia Re described crystal reaction tube (1) be not less than 800 ℃ but be not higher than 1100 ℃, and the temperature of described basic substrate (7) be higher than 1150 ℃ but be not higher than 1250 ℃.

43. method according to the manufacturing GaN crystal (12) of claim 24, wherein during the described GaN crystal of growth (12), externally the temperature of Jia Re described crystal reaction tube (1) be not less than 800 ℃ but be not higher than 950 ℃, and the temperature of described basic substrate (7) be higher than 1150 ℃ but be not higher than 1250 ℃.

44. method of making GaN crystal (12), this method is by in crystal reaction tube (1), the reaction of the material gas by comprising gallium halide gas and ammonia, growing GaN crystal (12) is made the GaN crystal on the surface of basic substrate (7), wherein at the growing period of described GaN crystal (12), the temperature of described basic substrate (7) is higher than 1100 ℃ and still is not higher than 1300 ℃.

45. method of making GaN crystal (12), this method is by in crystal reaction tube (1), the reaction of the material gas by comprising gallium halide gas and ammonia, growing GaN crystal (12) is made the GaN crystal on the surface of basic substrate (7), wherein at the growing period of described GaN crystal (12), the temperature of described basic substrate (7) is higher than 1150 ℃ and still is not higher than 1250 ℃.

46. a GaN crystalline substrate, it comprises the GaN crystal (12) that obtains by the method according to the manufacturing GaN crystal (12) of claim 24.

47. a product, it comprises the GaN crystalline substrate according to claim 46.

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