CN101081485A - Surface treatment method, nitride crystal substrate, semiconductor device, and method of manufacturing and semiconductor device - Google Patents
Surface treatment method, nitride crystal substrate, semiconductor device, and method of manufacturing and semiconductor device Download PDFInfo
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- CN101081485A CN101081485A CN 200710108825 CN200710108825A CN101081485A CN 101081485 A CN101081485 A CN 101081485A CN 200710108825 CN200710108825 CN 200710108825 CN 200710108825 A CN200710108825 A CN 200710108825A CN 101081485 A CN101081485 A CN 101081485A
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Abstract
A surface treatment method for a nitride crystal is a surface treatment method of chemically and mechanically polishing a surface of the nitride crystal (1). Oxide abrasive grains (16) are used. The abrasive grains (16) have a standard free energy of formation of at least -850 kJ/mol as a converted value per 1 mole of oxygen molecules and have a Mohs hardness of at least 4. The surface treatment method efficiently provides, for efficiently obtaining a nitride crystal substrate that can be used for a semiconductor device, the nitride crystal having the smooth and high-quality surface formed thereon.
Description
Technical field
The present invention relates to be used for the surface treatment method of element nitride crystal, this element nitride crystal is as for example substrate of the semiconductor devices of luminescent device, electronic device and semiconductor transducer.In addition, the present invention relates to utilize the element nitride crystal substrate of the surface treatment method acquisition that is used for element nitride crystal, and relate to semiconductor devices that comprises the element nitride crystal substrate and the method for making this semiconductor devices.
Background technology
Element nitride crystal, especially III group-III nitride crystal be GaN crystal and AlN crystal for example, and the material of the substrate of the semiconductor devices of luminescent device, electronic device and semiconductor transducer is very useful as for example being used for forming.Here, element nitride crystal refers to the crystal of being made by nitride, and as typically a kind of, it comprises III group-III nitride crystal.III group-III nitride crystal refers to the crystal that is made of III family element and nitrogen, and comprises for example Ga
xAl
yIn
1-x-yN crystal (0≤x, 0≤y, x+y≤1).
By the peripheral of finishing element nitride crystal and afterwards with this crystal cut obtaining the crystal that a slice has predetermined thickness, and grinding or lappingout should the surfaces, obtained the element nitride crystal substrate as semiconductor device substrates.Yet, this section, grinding or lappingout can cause the surface region of element nitride crystal to have the thick layer (work-affected layer) that influences of being processed and (refer to, because the grinding or the polishing of plane of crystal, the layer that in the surf zone of crystal, forms with disordered lattice, this also is suitable in following description), or element nitride crystal has the surface roughness of increase.Because the thickness of the layer that being processed of element nitride crystal substrate influences becomes big and because this surperficial roughness becomes big, the deterioration of substrate surface.In addition, the surface of epitaxially grown III group-III nitride crystal layer has bigger roughness on the element nitride crystal surface, and degree of crystallinity has worsened.Therefore, can not form high-quality semiconductor devices.
Thereby, as the method that forms the element nitride crystal substrate by element nitride crystal, use widely element nitride crystal is cut into the thin slice with predetermined thickness, grind or lappingout should the surface, step of going forward side by side (is for example carried out this surperficial dry etching (for example opening No.2001-322899 referring to the Japan Patent spy) or chemically mechanical polishing (being called CMP hereinafter), referring to U.S. Patent No. 6,596,079 and 6,488,767), remove thus and processed the layer that influences, and further reduce surface roughness.
Though the method on dry etching III group-III nitride crystalline substrates surface can be removed and be processed the layer that influences, be difficult to further reduce this surface roughness.
In addition, conventional CMP is pressed to element nitride crystal this polishing pad, the surface of polishing element nitride crystal simultaneously by the slurry that comprises than the abrasive particle that the hardness of polished element nitride crystal is low is provided to polishing pad.Yet, because element nitride crystal is hard and response is slow relatively, so conventional CMP is quite low aspect polishing velocity and efficient.
Summary of the invention
The purpose of this invention is to provide a kind of surface treatment method that is used for element nitride crystal, form level and smooth and high-quality element nitride crystal surface effectively, to obtain can be used in the element nitride crystal substrate of semiconductor devices effectively by this method.
The present invention is the surface treatment method on chemistry and machine glazed finish element nitride crystal surface, it utilizes the abrasive particle of oxide, this abrasive particle has at least-and the standard free energy of formation of 850kJ/mol is as the conversion value of per 1 mole oxygen molecule, and abrasive particle has and is at least 4 Mohs' hardness.
According to the surface treatment method of element nitride crystal of the present invention, abrasive particle is dispersed in the solvent with as slurry, and this pH value of slurry x and Eo+ value y (mV) can satisfy relation (i) and (ii):
Y 〉=-50x+1000 ... (i); With
y≤-50x+1900 ...(ii)。
In addition, this slurry can have and is at most 5 or be at least 9 pH.In addition, this abrasive particle can be to comprise to be selected from by Fe
2O
3, Fe
3O
4, NiO, ZnO, CoO, Co
3O
4, GeO
2, Ga
2O
3, In
2O
3, Cr
2O
3And SnO
2The abrasive particle of at least a chemical species of the group of forming.
According to the surface treatment method that is used for element nitride crystal of the present invention, can carry out any following processing at least: utilize neutral detergent to clean by the surface of the element nitride crystal of chemistry and machine glazed finish, utilize alkaline solution or acid solution polishing to clean by the surface of the element nitride crystal of chemistry and machine glazed finish by the surface of the element nitride crystal of chemistry and machine glazed finish with pure water.
According to the surface treatment method of element nitride crystal of the present invention, before chemistry and machine glazed finish, the surface of this element nitride crystal is ground or lappingout.
The present invention is the element nitride crystal substrate that obtains by aforesaid surface treatment method.Element nitride crystal substrate of the present invention can have the surface roughness Ry that is at most 30nm and/or the surface roughness Ra of 3nm at the most.In addition, by { 0001} crystal face, { 11-20} crystal face, { 01-12} crystal face, { 10-10} Jinping face, { 10-11} crystal face, { the 11-21} crystal face and { any one oblique angle that forms in the 11-22} crystal face can be at most 15 ° of the first type surface of element nitride crystal substrate and wurtzite structure.
The present invention is the element nitride crystal substrate with epitaxial loayer, and it is included in the III group iii nitride layer of the one deck at least that forms by epitaxial growth at least one first type surface of element nitride crystal substrate.In addition, the present invention comprises the element nitride crystal substrate and the semiconductor devices of the III group iii nitride layer of one deck at least of forming at least one first type surface of element nitride crystal substrate.In addition, the present invention is a kind of manufacture method with element nitride crystal substrate of epitaxial loayer, selects above-mentioned element nitride crystal substrate as substrate, and the III group iii nitride layer of one deck at least of growing at least one first type surface of this nitride.In addition, the present invention is a method of making semiconductor devices, selects above-mentioned element nitride crystal substrate as substrate, and the III group iii nitride layer of one deck at least of growing at least one first type surface of this nitride.
According to the present invention, can be provided for the surface treatment method of element nitride crystal, form level and smooth and high-quality element nitride crystal surface effectively by this method, to obtain can be used for the element nitride crystal substrate of semiconductor devices effectively.
In conjunction with the accompanying drawings, in following detailed description the in detail of the present invention, above-mentioned purpose, feature, aspect and advantage with other of the present invention will become more obvious.
Description of drawings
Fig. 1 is the schematic section that the embodiment of the surface treatment method that is used for element nitride crystal according to the present invention is shown.
Fig. 2 is the schematic section that another embodiment of the surface treatment method that is used for element nitride crystal according to the present invention is shown.
Fig. 3 is the schematic section that the embodiment of the polishing that utilizes alkaline solution or acid solution that can be included in the surface treatment method that is used for element nitride crystal according to the present invention is shown.
Fig. 4 is the schematic section that the embodiment of the grinding that can be included in the surface treatment method that is used for element nitride crystal according to the present invention is shown.
Fig. 5 is the schematic cross-section face that the embodiment of the lappingout that can be included in the surface treatment method that is used for element nitride crystal according to the present invention is shown.
Fig. 6 is the schematic section that semiconductor device according to the invention embodiment is shown.
The specific embodiment
First embodiment
According to the present invention, with reference to figure 1, the embodiment that is used for the surface treatment method of element nitride crystal is the surface treatment method on the surface of chemistry and machine glazed finish element nitride crystal 1, and this embodiment is characterised in that and uses oxide abrasive grain 16, the standard free energy of formation of abrasive particle 16 is at least-850kJ/mol, it is the conversion value of 1 mole oxygen molecule, and the Mohs' hardness of abrasive particle 16 is at least 4.
In the present embodiment, chemistry and machine glazed finish (CMP) refers to chemistry and/or mechanically make will polished surface of the work smoothing hereinafter.For example,, rotate simultaneously around rotating shaft 15c, the slurry 17 that wherein is dispersed with abrasive particle 16 is supplied on the polishing pad 18 from slurry supply port 19 at the polishing pad 18 that is fixed on the panel 15 with reference to figure 1.On the crystal fixator 11 of fixing element nitride crystal 1, place weight 14 and crystal fixator 11 around its rotating shaft 11c rotation, simultaneously element nitride crystal 1 is pressed to polishing pad 18.In this mode, can chemistry and the surface of mechanically polishing element nitride crystal 1.Here, polishing refers to weak relatively load and makes surface smoothing and smooth technology, comprise from a spot of polishing of surface removal, and the polishing of the general workpiece fine finishining (finish) of wanting polished with opposing of this polishing.Form contrast with polishing, rough polishing is called lappingout.
In the present embodiment, element nitride crystal 1 refers to the crystal of being made by nitride, and as the typical case, comprises III group-III nitride crystal.III group-III nitride crystal refers to the crystal that is formed by III family element and nitrogen, and comprises for example Ga
xAl
yIn
1-x-yN crystal (0≤x, 0≤y, x+y≤1).
The abrasive particle that is used for the CMP of present embodiment is an oxide, has at least-standard free energy of formation of 850kJ/mol, and it is the conversion value in 1 mole oxygen molecule.By oxide make and have at least-this abrasive particle in the high standard free energy of formation (hereinafter for being called " standard free energy of formation of conversion ") of the conversion value of 1 mole oxygen molecule of 850kJ/mol has the strong oxidability to the element nitride crystal surface.Therefore, abrasive particle provides the high chemical polishing effect to the element nitride crystal surface.
Standard free energy of formation be also referred to as the standard gibbs generate can, it refers to element under the standard state of benchmark in standard state (1 * 10
5Pa) Gibbs energy of the isothermal (, being generally 298.15K here) of 1 mole of material of generation (single element, compound) reaction changes, and with symbol Δ G
f 0Expression.Based on following formula (iv), by standard enthalpy of formation Δ H
f 0With standard formation entropy Δ S
f 0, calculate this amount.
ΔG
f 0＝ΔH
f 0-TΔS
f 0 ...(iv)。
Expression formula (iv) in, T represents absolute temperature.
Aforesaid standard free energy of formation Δ G
f 0Show by its definition, as by following formula (v) to (viii), depend on the Gibbs free of reaction of difference of the chemical valence " m " of M atom:
When m=1,2M (s)+(1/2) O
2(g) → M
2O (s) (v)
When m=2, M (s)+(1/2) O
2(g) → MO (s) is (vi)
When m=3,2M (s)+(3/2) O
2(g) → M
2O
3(s) (vii)
When m=4, M (s)+O
2(g) → MO
2(s) (viii)
More specifically, when the chemical valence of M atom was respectively 1,2,3 and 4, Gibbs free was to produce 1 mole of M respectively
2O, MO, M
2O
3And MO
2The Gibbs free of the reaction of molecule.Therefore, it is different being included in the quantity of 1 mole of M atom in the oxide molecule and the quantity of oxygen atom.
Therefore, M atom and the 1 mole oxygen molecular reaction standard free energy of formation when generating MpOq (p, q are positive integers) is defined as standard free energy of formation (Zhuan Huan standard free energy of formation just) with 1 mole oxygen molecule, and with symbol Δ G
F02 0Expression.That is to say that the standard free energy of formation of conversion shows as the free energy change by the reaction shown in the following formula (ix) to (xii) (wherein the chemical valence of M atom is m).
When m=1,4M (s)+O
2(g) → 2M
2O (s) (ix)
When m=2,2M (s)+O
2(g) → 2MO (s) is (x)
When m=3, (4/3) M (s)+O
2(g) → (2/3) M
2O
3(s) (xi)
When m=4, M (s)+O
2(g) → MO
2(s) (xii)
Therefore, consider standard free energy of formation Δ G
f 0Expression formula (v) the coefficient of oxygen molecule in (xii) calculates the standard free energy of formation Δ G of conversion
F02 0(v) in (xii), symbol that illustrates after each single element or compound (s) and symbol (g) represent that this single element or compound are in solid-state or gaseous state respectively in expression formula.
With regard to strengthening the chemical polishing effect, the standard free energy of formation of the conversion of abrasive particle is preferably at least-the 800kJ/ mole, more preferably at least-and 700kJ/mol, and more preferably at least-600KJ/mol.If the standard free energy of formation of the conversion of abrasive particle at least-700kJ/mol, then can use the abrasive particle of small grain size and soft, and need not to reduce considerably polishing velocity, and can polish plane of crystal effectively and in element nitride crystal, do not form and processed the layer that influences.
The abrasive particle that is used for the CMP of present embodiment has and is at least 4 Mohs' hardness.Mohs' hardness is at least 4 abrasive particle has mechanical polishing effect to the surface of element nitride crystal.Aspect enhancing machine glazed finish effect, the Mohs' hardness of abrasive particle preferably is at least 5, more preferably is at least 7, and more preferably is at least 8.Especially, when abrasive particle has 7 or during higher Mohs' hardness, processed the layer that influences and have bigger thickness, polishing velocity is higher simultaneously.
Be generally used for polishing abrasive particle with lappingout by for example diamond, SiC, BN, Al
2O
3, SiO
2, ZrO
2Make.Aspect enhancing machine glazed finish effect, select the abrasive particle of making by any these chemical species.Aspect the increase polishing velocity, use the abrasive particle of high rigidity and coarsegrain.Aspect reducing surface roughness and/or being processed the layer that influences, use the abrasive particle of soft and small grain size.Shorten polishing time simultaneously in order to obtain level and smooth and high-quality surface, begin the abrasive particle of small grain size then, utilize polytype abrasive particle to polish with a plurality of steps from the abrasive particle of coarsegrain.
Owing to need very high surface quality for semiconductor device substrates, so mainly use SiO
2The abrasive particle polished substrate.As for SiO
2Abrasive particle can obtain spherical abrasive particle and can carry out complicated granularity control.Therefore, can reduce to be processed influence the layer and can make surface smoothing.For polished glass, mainly use CeO
2Abrasive particle.Can be using CeO
2The abrasive particle polished glass is regarded the wherein polishing of the Si of Ce replacement glass as.
Yet, because element nitride crystal chemically stable and have high hardness, only use above-mentioned common abrasive particle that chemical polishing effect to element nitride crystal can not be provided.For example, diamond abrasive grain, SiC abrasive particle and BN abrasive particle are not oxides, and do not have the chemical polishing effect that obtains from the oxidation to the surface of element nitride crystal.In addition, although Al
2O
3Abrasive particle, SiO
2Abrasive particle, CeO
2Abrasive particle and ZrO
2Abrasive particle all is an oxide, but the standard free energy of formation ratio-850kJ/mol of conversion is little.Therefore, the chemical polishing effect that obtains from the oxidation to the element nitride crystal surface is quite low.
About the abrasive particle that uses in the present embodiment, as long as this abrasive particle is an oxide, have at least-standard free energy of formation of the conversion of 850kJ/mol, and have and be at least 4 Mohs' hardness, this abrasive particle is not limited to specific abrasive particle.Yet preferred strengthening aspect surface quality and the polishing velocity, abrasive particle comprises and being selected from by Fe
2O
3, Fe
3O
4, NiO, ZnO, CoO, Co
3O
4, GeO
2, Ga
2O
3, In
2O
3, Cr
2O
3And SnO
2At least a chemical species in the group that constitutes.
Fe
2O
3The standard free energy of formation of conversion be 6 for-570kJ/mol and Mohs' hardness, Fe
3O
4The standard free energy of formation of conversion be 6 for-580kJ/mol and Mohs' hardness, the standard free energy of formation of the conversion of NiO is 5.5 for-500kJ/mol and Mohs' hardness, the standard free energy of formation of the conversion of ZnO is 4 for-720kJ/mol and Mohs' hardness, the standard free energy of formation of the conversion of CoO is 5 for-510kJ/mol and Mohs' hardness, Co
3O
4The standard free energy of formation of conversion be 5 for-470kJ/mol and Mohs' hardness, GeO
2The standard free energy of formation of conversion be 5 for-570kJ/mol and Mohs' hardness, Ga
2O
3The standard free energy of formation of conversion be 5 for-740kJ/mol and Mohs' hardness, In
2O
3The standard free energy of formation of conversion be 5 for-770kJ/mol and Mohs' hardness, Cr
2O
3The standard free energy of formation of conversion be 8.5 for-770kJ/mol and Mohs' hardness, SnO
2The standard free energy of formation of conversion be 6.8 for-600kJ/mol and Mohs' hardness.
According to the surface treatment method of the element nitride crystal in the present embodiment, with reference to figure 1, abrasive particle 16 is dispersed in the solvent to be used as slurry 17.Preferably, the value y (mV) of the value x of the pH of slurry 17 and Eo+ (being referred to as ORP hereinafter) satisfy following relation (i) and (ii) both.
y≥-50x+1000 ...(i)
y≤-50x+1900 ...(ii)
Particularly, the slurry in the present embodiment 17 has the abrasive particle 16 that is dispersed in as mentioned above as in the water that disperses medium.The content of abrasive particle 16 is not limited to certain content in the slurry 17.Aspect effective polishing on element nitride crystal surface, slurry content is preferably and accounts for quality at least 1% (by mass) and account for quality 30% at the most, more preferably accounts for quality at least 2% and be at most to account for quality 20%.
ORP refers to the energy level of being determined by the poised state between the Oxidizing and Reducing Agents that coexists as in the solution (current potential).By measuring the ORP that obtains is the value relevant with reference electrode.For same solution, dissimilar reference electrodes provides obvious different measuring.In general paper, under many situations, use standard hydrogen electrode (NHE) conduct with reference to electrode.Here ORP is shown as the value with respect to the standard hydrogen electrode (NHE) that is used as reference electrode.
When the pH of the slurry in the present embodiment 17 value x and ORP value y (mV) satisfy concern y＜-during 50x+1000, the polishing velocity on the oxidability a little less than slurry 17 has and the surface of element nitride crystal 1 is slow.On the contrary, when satisfy concern y＞-during 50x+1900, the oxidability of slurry 17 is crossed the deep-etching effect that causes by force for example polishing pad and this polishing tool of surface plate (surface plate), causes being difficult to realize stable CMP.
Further increasing aspect the polishing velocity, preferred satisfy concern y 〉=-50x+1300.In other words, the pH value x of preferred slurry 17 and ORP value y (mV) are satisfied by expression formula (ii) and the following relation of (iii) representing.
y≤-50x+1900 ...(ii)
y≥-50x+1300 ...(iii)
The acid (for example hydrochloric acid and sulfuric acid) and the alkali (for example KOH and NaOH) that are included in the common slurry have the weak oxide ability for chemically stable element nitride crystal surface.Therefore, preferred, the slurry in the present embodiment comprises the oxidant that is added on wherein, and has high ORP thus, just the oxidability of Zeng Jiaing.The amount of the oxidant that regulate to add so as the pH value x of slurry 17 and ORP value y (mV) satisfied two concern y 〉=-50x+1000 (expression formula (i)) and y≤-50x+1900 (expression formula (ii)).
The oxidant that adds slurry to is not limited to specific oxidant.Yet, aspect the increase polishing velocity, for example, preferably use for example hypochlorous acid, the chlorinated isocyanuric acid (chlorinated isocyanuricacid) of TCCA (trichloroisocyanuric acid) for example, the chlorinated isocyanuric acid salt (chlorinated isocyanurate) of DCCNa (sodium dichloroisocyanurate) for example, the permanganate of potassium permanganate for example, the bichromate of potassium bichromate for example, the bromate of potassium bromate for example, the thiosulfate of sodium thiosulfate for example, the persulfate of ammonium persulfate and potassium peroxydisulfate for example, nitric acid, oxygenated water and ozone.Can use these oxidants maybe can use two or more oxidants separately.
Preferably, the pH of slurry 17 in the present embodiment is at most 5 or be at least 9.Have pH and be 5 following acid slurry or have pH be 9 or above alkaline slurry can contact the oxidation of element nitride crystal with the layer 1a that promote being processed of element nitride crystal and influence, increased polishing velocity thus.Given this, the pH of preferred slurry 17 is at most 4 and more preferably be at most 2.Also the pH of preferred slurry 17 is at least 10.
Bronsted lowry acids and bases bronsted lowry as the pH conditioning agent is not limited to specific bronsted lowry acids and bases bronsted lowry.For example, can use inorganic acid for example hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and carbonic acid, organic acid is formic acid, acetic acid, citric acid, malic acid, tartaric acid, butanedioic acid, phthalandione and fumaric acid for example, and alkali is KOH, NaOH, NH for example
4OH and amine maybe can use the salt that comprises these acid or alkali.In addition, can add above-mentioned oxidant and regulate pH.
Especially, as the pH conditioning agent, by using aforesaid any organic acid and/or their salt, and compare for the aforesaid any inorganic acid of use that obtains identical pH and/or the situation of their salt, can obtain higher polishing velocity for element nitride crystal.Aspect the increase polishing velocity, preferred, described organic acid and/or their salt are that each molecule comprises the carboxylic acid of two or more carboxyls and/or their salt.For example, preferred dicarboxylic acids is malic acid, butanedioic acid, phthalandione and tartaric acid.Preferred tricarboxylic acids for example is a citric acid.Therefore, preferred, slurry comprises aforesaid abrasive particle, oxidant, organic acid and/or their salt.
Second embodiment
According to the present invention, with reference to figure 2, another embodiment that is used for the surface treatment method of element nitride crystal is the surface treatment method on the surface of chemistry and machine glazed finish element nitride crystal 1.Use oxide abrasive grain 26, the standard free energy of formation of the conversion of abrasive particle 26 is at least-850kJ/mol, and the Mohs' hardness of abrasive particle 26 is at least 4.Here, the abrasive particle in the present embodiment is similar to the abrasive particle among first embodiment.
CMP in the present embodiment is characterised in that, the adhesive by solid-state use directly uses or bonded-abrasive, and it is dry method CMP to carry out CMP, rather than it is wet method CMP to utilize abrasive particle in liquid form among first embodiment such as the slurry to carry out CMP.Abrasive particle in the present embodiment has at least-standard free energy of formation of the conversion of 850kJ/mol.Therefore, even abrasive particle is not the form of the slurry resembling among first embodiment, abrasive particle self also has the high chemical polishing effect to the element nitride crystal surface, and this effect is produced by oxidation.In addition, the abrasive particle in the present embodiment has and is at least 4 Mohs' hardness, and also has the machine glazed finish effect thus except the chemical polishing effect.Therefore, the polishing of aforesaid dry method form also can be used for carrying out the CMP to element nitride crystal.
With reference to figure 2, for example, can the CMP that carry out in the present embodiment as described below.Abrasive particle 26 is by bond 27 fixing fixing to form (fixed) abrasive particle body 28, for example grinding agent, polishing pad and sand belts.When the bonded-abrasive body 28 on being fixed to surface plate 25 rotates around rotating shaft 25c, fixed of the rotating shaft 21c rotation of the crystal fixator 21 of element nitride crystal 1 and top placement weight 24, and element nitride crystal 1 is pressed towards this bonded-abrasive body 28 around it.In this mode, can chemistry and the surface of mechanically polishing element nitride crystal 1.
As long as energy bonded-abrasive 26, bond 27 is not limited to specific bond.Aspect abrasive particle confining force and intensity, preferably use for example phenolic resins (phenol resin), polyimide resin, polyamide, alkyd resin, polyvinyl alcohol resin, polyurethane resin.The form of bonded-abrasive body 28 also is not limited to specific abrasive particle body, and can be any form, for example grinding agent, polishing pad or sand belt.
By the dry method CMP in the present embodiment, not only can utilize as shown in Figure 2 the bonded-abrasive type CMP of the bonded-abrasive body 28 that produces by bond 27 bonded-abrasives 26, utilization during CMP from the semifixed abrasive particle type CMP of the abrasive particle 26 of bonded-abrasive body 28 feed-ins and former state utilize the free abrasive particle type CMP of abrasive particle.In addition, for free abrasive particle type CMP, can use the Compostie abrasive particles that generates by bond combination abrasive particle.The bond that is used to make up abrasive particle is not limited to specific kind.Aspect the abrasive particle confining force, preferably use alkyd resin, polyvinyl alcohol resin etc.
For the surface treatment method among first or second embodiment, utilize neutral detergent to clean the chemistry of element nitride crystal and the surface of machine glazed finish after the preferred CMP.By utilizing the scouring of neutral detergent, can remove the impurity that attaches to the element nitride crystal surface during the CMP metallic element of abrasive particle (for example from) easily.In addition, not only the impurity that attaches to substrate main surface can be removed, the impurity that attaches to the substrate peripheral side surface can be removed in addition.
The neutral detergent here refers to has the almost washing agent of neutral pH (for example, pH is in 5 to 8.5 scope).Use the mode of neutral detergent to be not limited to specific mode.Aspect the high cleaning effect and easy removal of washing agent, the preferred aqueous solution that uses with water dilution neutral detergent.Preferably, the concentration of neutral detergent is at least 0.01 quality % and is at most 2 quality %.Neutral detergent can be mixed with acid or alkali cleans effect with further enhancing.
Scouring refers to by pushing rotary brush (use has the brush of bristle or sponge) and shifting brush, simultaneously cleaning fluid is coated to brush to plane of crystal, cleans the impurity that attaches to plane of crystal.Can clean by cloth and polishing pad artificially.
CMP in first embodiment (wet method CMP) utilizes under the situation of neutral detergent scouring afterwards, and it is effective cleaning before the substrate drying after wet method CMP.
For the surface treatment method among first or second embodiment, utilize alkali or acid solution after the preferred CMP, to the surface finish of the element nitride crystal of chemistry and machine glazed finish.By utilizing the polishing fluid (for example alkaline solution or acid solution) that does not contain as the solids of abrasive particle to polish, can easily remove and during CMP, attach to the lip-deep impurity of element nitride crystal.
The finishing method here is not limited to specific finishing method.For example, with reference to figure 3, when the polishing pad 38 on being fixed to surface plate 35 rotates around rotating shaft 35c, polishing fluid 37 is provided on the polishing pad 38 from polishing fluid charging aperture 39, fixedly the crystal fixator 31 of element nitride crystal 1 and top placement weight 34 rotates around its rotating shaft 31c, and element nitride crystal 1 is pressed towards polishing pad 38.In this mode, can remove element nitride crystal 1 lip-deep impurity effectively.
Preferably, polishing fluid 37 is that pH is at most 5 acid solution or pH and is at least 9 alkaline solution.The acid solution here is not limited to specific acid solution, and preferably use for example solution of the inorganic acid of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, the organic acid solution of formic acid, acetic acid, citric acid, malic acid, tartaric acid, butanedioic acid, phthalandione, fumaric acid for example, or comprise at least two kinds of above-mentioned inorganic acids and organic acid solution.Although alkaline solution is not limited to specific alkaline solution, preferably use for example KOH, NaOH, NH
4The aqueous slkali of OH and amine.
In addition, for the surface treatment method of the element nitride crystal in the present embodiment, preferably after CMP, clean the surface of the element nitride crystal of chemistry and machine glazed finish with pure water.By cleaning the element nitride crystal surface, can remove the impurity that during CMP, attaches to the element nitride crystal surface with pure water.The method of cleaning element nitride crystal with pure water is not limited to specific method.Effectively removing by mechanism aspect the impurity, preferably use the method as method for suppersonic cleaning or scouring method.
In addition, for the surface treatment method of the element nitride crystal among first or second embodiment, can be after CMP with neutral detergent clean, with alkalescence or acid solution polishing and the combination of cleaning with pure water.Three kinds are cleaned or how glossing should make up and be not limited to specific combination.Yet, effectively and most possibly removing aspect the lip-deep impurity of element nitride crystal by removing from those impurity of alkaline solution, acid solution or neutral detergent, preferably the step of cleaning with pure water is final step.
For example, may there be such method, cleaning with pure water with the neutral detergent scouring or after according to this method with alkalescence or acid solution polishing, and such method, carry out with following order according to this method: clean with neutral detergent, polish and clean with pure water with alkalescence or acid solution.Especially under the situation of after with alkalescence or acid solution polishing, cleaning,, preferably use method for suppersonic cleaning at effective ions of removing the metal ion in alkaline solution and the acid solution and comprising the light element of atomicity 1 to 18 with pure water.
Strengthening aspect the cleaning quality/ability of cleaning, cleaning with alkalescence or acid solution polishing with pure water with neutral detergent, the metallic element that preferably is contained in the abrasive particle that is used for CMP has high ionization tendency, and preferred ionization tendency is than the height of H.
About the surface treatment method of the element nitride crystal among first or second embodiment,, preferably before CMP, carry out the surface grinding or the lappingout of element nitride crystal 1 with reference to figure 1,4 and 5.By being combined in the surface grinding or the lappingout of the element nitride crystal that carries out before the CMP, can increase the polishing velocity on element nitride crystal surface and can form level and smooth and high-quality element nitride crystal surface.
The grinding here refers to removes this surface roughly so that the technology of the thickness of this surface smoothing and/or adjusting crystal.With reference to figure 4, for example, when comprising that the grinding agent 42 by the fixing abrasive particle of bond is fixed to grinding agent metal base 43, and when grinding agent rotates around rotating shaft 43c, grinding agent offered be fixed to crystal fixator 41 and around the surface of the element nitride crystal 1 of its rotating shaft 41c rotation, the surface of downcutting element nitride crystal 1 thus is so that this surface smoothing, and this is known as grinding.
The lappingout here refers to the rough polishing on surface.With reference to figure 5, for example, when rotating shaft 55c when rotation of surface plate 55 around it, the slurry 57 that comprises the abrasive particle 56 that is dispersed in wherein is provided on the surface plate 55 from slurry feed mouth 59, fixedly the crystal fixator 51 of element nitride crystal 1 and top placement weight 54 is around its rotating shaft 51c rotation, and element nitride crystal 1 is pressed towards surface plate 55, makes the surface smoothing of element nitride crystal 1 thus.In this lapping technique, do not use abrasive particle to be dispersed in wherein slurry, can make the grinding agent rotation that has with the abrasive particle of binder course compacting, and press to the surperficial (not shown) of element nitride crystal with the polishing element nitride crystal.
The 3rd embodiment
With reference to figure 1,2 and 6, the embodiment of element nitride crystal substrate of the present invention is the substrate by the element nitride crystal 1 of the manufacturing of the surface treatment method among first or second embodiment.By handle the surface of element nitride crystal 1 according to the surface treatment method among first or second embodiment, obtained element nitride crystal substrate 610, it has level and smooth and high-quality surface and is suitable for substrate as semiconductor devices.
For the element nitride crystal substrate in the present embodiment, under the condition of the surface treatment method in first or second embodiment and utilize its combination, can obtain surface roughness Ry and be at most the element nitride crystal substrate of 30nm and/or surface roughness Ra and be the element nitride crystal substrate of 3nm at the most.
Preferably, the element nitride crystal substrate in the present embodiment has the surface roughness Ry of 30nm at the most.Here, following definite surface roughness Ry.From coarse curved surface, on the direction of mean level of the sea (average plane), remove 10 μ m * 10 μ m (=100 μ m
2) a part of benchmark area, and determine to remove the distance from the mean level of the sea to the top of part and the summation of the distance from the mean level of the sea to the lowest trough.This summation is surface roughness Ry.When the element nitride crystal substrate has 30nm or following surface roughness Ry, can on the surface of element nitride crystal substrate, form form and the good epitaxial loayer of degree of crystallinity.Given this, more preferably this element nitride crystal substrate has the surface roughness Ry of 10nm at the most.Surface roughness Ry can measure by AFM (being called AFM hereinafter).
In addition, preferred, the element nitride crystal substrate in the present embodiment has the surface roughness Ra of 3nm at the most.Here, following definite surface roughness Ra.From coarse curved surface, on the direction of mean level of the sea, remove a part of benchmark area of 10 μ m * 10 μ m.Determine the summation of absolute value and use the benchmark area that this summation is average from mean level of the sea to the distance of removing each plane of partly measuring.The gained result is a surface roughness Ra.When the element nitride crystal substrate has 3nm or following surface roughness, can on the surface of this element nitride crystal substrate, form form and the good epitaxial loayer of degree of crystallinity.Given this, preferred, the element nitride crystal substrate has the surface roughness Ra of 1nm at the most.Surface roughness Ra can be measured by AFM.
Preferably, the major surfaces in parallel of the element nitride crystal substrate in the present embodiment is in { 0001} face, { 11-20} face, { 01-12} face, { 10-10} face, { 10-11} face, { the 11-21} face and { some of 11-22} face perhaps are formed on { 0001} face, { 11-20} face, { 01-12} face, { 10-10} face, { 10-11} face, { the 11-21} face and { oblique angle between the 11-22} face is at most 15 ° of the first type surface of element nitride crystal substrate and wurtzite structure of wurtzite structure.Here, { the 0001} face is also referred to as the c-face and refers to (0001) face and its equivalent face.{ the 11-20} face is also referred to as the a-face and refers to (11-20) face and its equivalent face.{ the 01-12} face is also referred to as the r-face and refers to (01-12) face and its equivalent face.{ the 10-10} face is also referred to as the m-face and refers to (10-10) face and its equivalent face.{ the 10-11} face is also referred to as the s-face and refers to (10-11) face and its equivalent face.{ the 11-21} face refers to (11-20) face and its equivalent face.{ the 11-22} face refers to (11-22) face and its equivalent face.
Element nitride crystal with wurtzite structure has polarity on [0001] direction (c direction of principal axis).Here, the c axle is called pole axis.The face vertical with pole axis (c axle) is called pole-face.In other words, pole-face is defined in perpendicular to the face that occurs polarization on the pole-face direction.In addition, the face that is parallel to pole axis (c axle) refers to non-pole-face.In addition, not vertical but be called the half-shadow face with face that pole axis intersects with pole axis (c axle).Semiconductor devices, for example utilize its first type surface be non-pole-face (for example, 10-10} face (m-face) and 11-20} face (a-face)) and the LED and the LD (laser diode) of element nitride crystal substrate, can have high luminous efficacy.In addition, when current density that increase applies, can suppress the blue shift (moving) of emission wavelength towards shorter wavelength.In addition, in the time will preparing semiconductor devices, if wish the epitaxial loayer of growth high-crystal quality on the first type surface of element nitride crystal substrate, then preferred this first type surface is that { 10-11} face (s-face), { 01-12} face (r-face), { the 11-21} face, { the 11-22} face, they are half-shadow faces.In the time will preparing LD, since the end face of resonator preferably have cleavage character 10-10} face (m-face) or 0001} face (c-face), thus preferred use its first type surface for example with 10-10} face (m-face) vertical (for example first type surface be 11-20} face (a-face), the 11-21} face, the 11-22} face) or with 0001} face (c-face) vertical (first type surface for example be 10-10} face (m-face), 11-20} face (a face)) and the element nitride crystal substrate.
By this oblique angle of 15 ° at the most is provided, it is formed in the angle between in the crystal face of the first type surface of element nitride crystal substrate and above-mentioned wurtzite structure one, is convenient to form on the element nitride crystal substrate form and the good epitaxial loayer of degree of crystallinity.Oblique angle above 15 ° causes the step part of epitaxial loayer possibly.The oblique angle is preferably at least 0.05 °.By at least 0.05 ° oblique angle is provided, can reduce the defective that is formed on the epitaxial loayer on the element nitride crystal substrate.Given this, the oblique angle is preferably at least 0.05 ° and 15 ° at the most, more preferably at least 0.1 ° and 10 ° at the most.By on the first type surface of element nitride crystal substrate, forming aforesaid form and the good epitaxial loayer of degree of crystallinity, can the good semiconductor devices of acquired character.In addition,, increased polishing velocity, and suppressed dislocation and concentrate main removal (predominant removal) in the zone that occurs, suppressing the generation of depression, and be convenient to the formation of smooth surface thus by aforesaid oblique angle is provided.
The 4th embodiment
With reference to figure 6, the embodiment with element nitride crystal substrate of epitaxial loayer of the present invention comprises III group iii nitride layer 650, and it comprises at least one layer that forms by epitaxial growth at least one first type surface of the element nitride crystal substrate 610 in the 3rd embodiment.Comprise that the III group iii nitride layer of one deck is the good epitaxial loayer of form and degree of crystallinity at least.On such epitaxial loayer, can further form the good other epitaxial loayer of form and degree of crystallinity, so that preparation has the good semiconductor devices of characteristic.
III group iii nitride layer 650 is not limited to specific layer, and can be, for example Ga
xAl
yIn
1-x-yN layer (0≤x, 0≤y, x+y≤1).In addition, the method of epitaxial growth III group iii nitride layer is not limited to specific method, and can be preferably, for example hydride vapor-phase epitaxy (being called HVPE hereinafter) method, molecular beam epitaxy (being called MBE hereinafter) method or Organometallic chemical vapor deposition (being called MOCVD hereinafter) method.Before epitaxial growth III group iii nitride layer, can in the equipment that carries out epitaxial growth technology, carry out the etching and/or the annealing of element nitride crystal substrate.
The 5th embodiment
With reference to figure 6, the embodiment of semiconductor devices of the present invention is a semiconductor devices 600, and this semiconductor devices 600 comprises the element nitride crystal substrate 610 of the 3rd embodiment and the III group iii nitride layer of being made up of the one deck at least at least one first type surface that is formed on element nitride crystal substrate 610 650.Semiconductor devices 600 in the present embodiment has III group iii nitride layer 650 at least one first type surface of this element nitride crystal substrate 610, this III group iii nitride layer 650 comprises the one deck at least by the good epitaxial loayer of form and degree of crystallinity.Therefore, semiconductor devices has good characteristic.
For example, the example of this semiconductor devices comprises luminescent device for example light emitting diode and laser diode, electronic device is rectifier, bipolar transistor, field-effect transistor and HEMT (HEMT) for example, and semiconductor transducer is temperature sensor, pressure sensor, radiation sensor and visible-ultraviolet radiation detector and SAW (surface wave) device for example.
The 6th embodiment
With reference to figure 6, the embodiment of the manufacture method of semiconductor devices of the present invention has following feature, the nitride-based semiconductor substrate 610 selected substrates of the 3rd embodiment as semiconductor devices, and at least one first type surface of element nitride crystal substrate 610, form the III group iii nitride layer of forming by one deck at least 650.By this manufacture method, at least one first type surface of the element nitride crystal substrate 610 of the 3rd embodiment, form one deck III group iii nitride layer 650 at least, it is the good epitaxial loayer of form and degree of crystallinity.Therefore, can obtain to have superperformance and long-life semiconductor devices.
Example
Based on following example and comparative example, provide the surface treatment method that is used for element nitride crystal, the element nitride crystal substrate that obtains by this surface treatment method and the more specifically description that comprises the semiconductor devices of this element nitride crystal substrate.
Example 1
＜1-1〉lappingout of n type GaN plane of crystal
Will be along the face parallel by the n type GaN crystal (adulterant: Si) cut into slices, of HVPE method growth to obtain the n type GaN crystalline substrates of diameter 50mm * thickness 0.5mm with (0001) face.With reference to figure 5, utilize wax that the c-face on the N atomic plane side of n type GaN crystalline substrates (element nitride crystal 1) ((000-1) face) has been attached to the crystal fixator of being made by ceramic material 51.On lappingout equipment (not shown), having assembled diameter is the surface plate 55 of 300mm.When the slurry 57 that will have the diamond abrasive grain 56 that is dispersed in wherein when slurry feed mouth 59 offers surface plate 55, surface plate 55 is around its rotating shaft 55c rotation, be provided at weight 54 on the crystal fixator 51 and make n type GaN crystalline substrates (element nitride crystal 1) is pressed to surface plate 55, and n type GaN crystalline substrates (element nitride crystal 1) is around the rotating shaft 51c rotation of crystal fixator 51.In this mode, lappingout should surface (the c-face on the Ga atomic plane side).
As surface plate 55, use copper surface plate or tin surfaces plate.Prepared three types diamond abrasive grain, just grit size is the diamond abrasive grain of 6 μ m, 3 μ m and 1 μ m.Along with lapping technique carries out, progressively used less grit size.Grinding pressure is 9.8kPa (100gf/cm
2) to 49kPa (500gf/cm
2).Each all is 30 rev/mins to 100 rev/mins for the velocity of rotation of n type GaN crystalline substrates (element nitride crystal 1) and surface plate 55.
By aforesaid lappingout, the surface treatment of n type GaN crystalline substrates is become the mirror ultrafinish face.After the lappingout, the layer that influences of being processed of n type GaN crystalline substrates has the thickness of 500nm, the surface roughness Ry of 25nm and the surface roughness Ra of 2.3nm.
＜1-2〉CMP of n type GaN plane of crystal
With reference to figure 1, with wax will be as mentioned above c-face ((000-1) face) on the N atomic plane side of n type GaN crystalline substrates (element nitride crystal 1) after the lappingout attach on the crystal fixator 11 of ceramic material.At the diameter that is assemblied on the polissoir (not shown) is on the surface plate 15 of 300nm, has placed polishing pad 18.When abrasive particle 16 being dispersed in wherein slurry 17 when slurry feed mouth 19 is provided to polishing pad 18, polishing pad 18 is rotated around rotating shaft 15c, weight 14 is placed on the crystal fixator 11 so that n type GaN crystalline substrates (element nitride crystal 1) is pressed to polishing pad 18, and n type GaN crystalline substrates (element nitride crystal 1) is around the rotating shaft 11c rotation of crystal fixator 11.In this mode, n type GaN crystalline substrates (the c-face on the Ga atomic plane side, (0001) face) is carried out CMP.
The polishing velocity height that is used for CMP, it is 1.5 μ m/hr.After CMP, the layer thickness that influences of being processed of n type GaN crystalline substrates is that 100nm, surface roughness Ry are that 10nm and surface roughness Ra are 1.2nm.The thickness of being processed the layer that influences of the cross section estimation n type GaN crystalline substrates by observing the crystal of cutting open along cleavage surface with transmission electron microscope (TEM).By observing the surface of the n type GaN crystalline substrates of 10 μ m * 10 mu m ranges by AFM (AFM), the surface roughness Ry and the surface roughness Ra of estimation n type GaN crystalline substrates.Being processed the layer that influences refers to by grinding or the polishing plane of crystal is formed in the surf zone of crystal and the layer of lattice disorder wherein.The existence and the thickness of layer can be discerned by tem observation.The thickness of the surface oxide layer of n type GaN crystalline substrates is 1.5nm after the CMP.Ratio in the surface of n type GaN crystalline substrates between Ga atom and the N atom is 50 atom %:50 atom %.Utilize the thickness of ellipsometer measurement surface oxide layer.By the ratio between the sub-spectrophotometric spectra of x ray electric light (XPS) estimation Ga atom and the N atom.
＜1-3〉comprise the manufacturing of the semiconductor devices of n type GaN crystalline substrates
With reference to figure 6, n type GaN crystalline substrates after the CMP is arranged in the MOCVD equipment, and on a first type surface (having carried out (0001) face of CMP on it) of n type GaN crystalline substrates (element nitride crystal substrate 610), form continuously by MOCVD: the thickness that is included in the n type semiconductor layer 620 is the n type GaN layer 621 (adulterant: be the n type Al of 150nm with thickness Si) of 1 μ m
0.1Ga
0.9N layer 622 (adulterant: Si), luminescent layer 640, the thickness that is included in the p type semiconductor layer 630 is the p type Al of 20nm
0.2Ga
0.8N layer 631 (adulterant: be the p type GaN layer 632 (adulterant: Mg) of 150nm Mg) with thickness.Luminescent layer 640 has multi-quantum pit structure, and each all has four GaN barrier layers of 10nm thickness and each all has three Ga of 3nm thickness in this structure
0.85In
0.15N trap layer is alternately stacked each other.
Then, on another first type surface ((000-1) face) of n type GaN crystalline substrates (element nitride crystal substrate 610), formed the laminated construction formed by the Au layer of the Ti layer of the Al layer of the Ti layer of 200nm thickness, 1000nm thickness, 200nm thickness and 2000nm thickness as first electrode 661.This electrode of heating is to make the n lateral electrode of 100 μ m diameters in blanket of nitrogen.On p type GaN layer 632, formed the laminated construction formed by the Au layer of the Ni layer of 4nm thickness and 4nm thickness as second electrode 662.This electrode of heating is to make the p lateral electrode in inert gas atmosphere.This laminated body is sliced into the chip of 400 μ m * 400 μ m.Afterwards, the solder layer 670 with AuSn is attached to the p lateral electrode on the conductor 682.In addition, be configured to the semiconductor devices 600 of LED with manufacturing in conjunction with n lateral electrode and conductor 681 with lead 690.
At the electric current that applies is that the light that utilizes integrating sphere (integrating sphere) to measure resulting LED (semiconductor devices 600) under the condition of 20mA is exported.The light output of LED in the present embodiment is expressed as 1.0 relative intensity, and shows each relative intensity of other embodiment below.These results in table 1, have been summarized.
Example 2-6, comparative example 1-5
Carried out lappingout and CMP, and except the abrasive particle that is used in the slurry among the CMP, pH and the ORP shown in the table 1, made semiconductor devices similarly with example 1.The result is summarized in the table 1.As for the oxidant in the table 1, DCIA-Na represents DCCNa." fracture hole (fracture hole) " about comparative example 4 refers to conduct owing to the mechanical load among the CMP causes the small hole that the result produced of breaking of plane of crystal.Utilize interference of light talysurf (light interference profilometer) to measure the degree of depth of resolving ceasma.Many fractures hole has the 50nm or the above degree of depth.
Table 1
| C.E.1 | C.E.2 | C.E.3 | C.E.4 | C.E.5 | E.1 | E.2 | E.3 | E.4 | E.5 | E.6 | ||||
| C M P | Abrasive particle | The chemical species that comprises | Al 2O 3 | SiO 2 | CeO 2 | SiC | CuO | Cr 2O 3 | Fe 2O 3 | Fe 3O 4 | NiO | ZnO | Co 3O 4 | |
| Mohs' hardness | 9 | 7 | 5 | 9.5 | 3.5 | 8.5 | 6 | 6 | 5.5 | 4 | 5 | |||
| The standard free energy of formation (kJ/mol) of conversion | -1130 | -920 | -1030 | - | -340 | -770 | -570 | -580 | -500 | -720 | -470 | |||
| Granularity (μ m) | 0.5 | 0.2 | 0.2 | 9.5 | 1.0 | 0.5 | 0.3 | 0.5 | 1.0 | 2.0 | 1.0 | |||
| Oxidant | DCIA -Na | DCIA -Na | DCIA -Na | DCIA -Na | DCIA -Na | DCIA -Na | DCIA -Na | DCIA -Na | DCIA -Na | DCIA -Na | DCIA -Na | |||
| Acid, alkali, salt (pH conditioning agent) | HNO 3 | HNO 3 | HNO 3 | HNO 3 | HNO 3 | HNO 3 | HNO 3 | HNO 3 | HNO 3 | HNO 3 | HNO 3 | |||
| The pH of slurry | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | |||
| The ORP of slurry (mV) | 980 | 980 | 980 | 980 | 980 | 980 | 980 | 980 | 980 | 980 | 980 | |||
| Polishing velocity (μ m/hr) | 0.8 | 0 | 0 | 0.9 | 0 | 1.5 | 0.5 | 0.5 | 0.4 | 0.3 | 0.6 | |||
| Surface assessment after the CMP | Surface roughness Ry (nm) | 9.1 | 11 | 25 | 150 | 20 | 10 | 4.0 | 4.5 | 6.2 | 5.6 | 20 | ||
| Surface roughness Ra (nm) | 0.86 | 0.91 | 2.8 | 9.5 | 1.8 | 1.2 | 0.42 | 0.48 | 0.53 | 0.45 | 2.1 | |||
| Processed the thickness (nm) of the layer that influences | 300 | 500 | 500 | 1200 | 500 | 100 | - | - | - | - | - | |||
| Remarks | The fracture hole | |||||||||||||
| The relative light output intensity of LED | - | - | - | - | - | 1.0 | 2.8 | 2.1 | 1.6 | 1.7 | 2.2 | |||
*DCIA-Na: DCCNa
*C.E.: comparative example, E: example
Example 7-12
Carry out lappingout and CMP, and except abrasive particle, pH and the ORP of the slurry that is used for CMP be shown in the table 2 those, make semiconductor devices similarly with example 1.In table 2, summarized the result.As for the oxidant in the table 2, DCIA-Na represents DCCNa.As for the chemical species that the abrasive particle in the table 2 comprises, the Fe of example 11
2O
3+ SnO
2Expression chemical species Fe
2O
3And SnO
2Mixture, and the NiOFe of example 12
2O
3Expression is by chemical species NiO and Fe
2O
3The synthesis oxide NiFe that forms
2O
4
Example 13, comparative example 6
＜2-1〉grinding on n type GaN crystalline substrates surface
Along the n type GaN crystal of the planar slice that is parallel to (0001) face by HVPE growth (adulterant: Si), to obtain the n type GaN crystalline substrates of diameter 50mm * thickness 0.5mm.With reference to figure 4, the c-face on the N atomic plane side of n type GaN crystalline substrates (element nitride crystal 1) ((000-1) plane) is attached to ceramic crystal fixator 21 with wax.As grinder, use (in-feed) type of insertion grinder.As grinding agent 42, used the ceramic diamond abrasive of the annular of overall diameter 80mm * width 5mm.N type GaN crystalline substrates (element nitride crystal 1) is fixed to crystal fixator 41 and rotates around its rotating shaft 41c, the grinding agent 42 that is fixed to grinding agent metal base 43 simultaneously is round its rotating shaft 43c rotation, and grinding agent 42 supplies to the surface of n type GaN crystal.In this way, ground the surface (the c-face on the Ga atomic plane side, (0001) face) of n type GaN crystal.Prepared and comprised that wear particle size is four types the diamond abrasive of 15 μ m, 5 μ m, 3 μ m and 1 μ m separately, and, progressively used littler wear particle size along with grinding is carried out.This grinding provides the surface of mirror finish (mirror finished) to the surface of n type GaN crystal.It is that 1500nm, surface roughness Ry are that 79nm and surface roughness Ra are the layer that being processed of 6.2nm influences that n type GaN crystalline substrates after the grinding has thickness.
＜2-2〉CMP on GaN crystalline substrates surface
Except having used slurry, the n type GaN crystalline substrates of correct grinding has been carried out CMP in the example 1 with abrasive particle as shown in table 2, pH and ORP.
＜2-3〉comprise the manufacturing of the semiconductor devices of n type GaN crystalline substrates
After above-mentioned CMP, n type GaN crystalline substrates is arranged in the MOCVD equipment, make semiconductor devices to be similar to example 1.Table 2 has always been summarized this result.As for the oxidant in the table 2, " TCIA " represents TCCA.
Table 2
| E.7 | E.8 | E.9 | E.10 | E.11 | E.12 | C.E.6 | E.13 | |||
| C M P | Abrasive particle | The chemical species that comprises | SnO 2 | GeO 2 | Ga 2O 3 | In 2O 3 | Fe 2O 3+ SnO 2 | NiO· Fe 2O 3 | Al 2O 3 | Cr 2O 3 |
| Mohs' hardness | 6.8 | 5 | 5 | 5 | 6， 6.8 | 5 | 9 | 8.5 | ||
| The standard free energy of formation (kJ/mol) of conversion | -600 | -570 | -740 | -700 | -570， -600 | -560 | -1130 | -770 | ||
| Granularity (μ m) | 1.0 | 1.0 | 1.0 | 2.0 | 1.0， 1.0 | 3.0 | 0.5 | 0.5 | ||
| Oxidant | DCIA -Na | DCIA -Na | DCIA -Na | DCIA -Na | DCIA -Na | DCIA -Na | TCIA | TCIA | ||
| Acid, alkali, salt (pH conditioning agent) | HNO 3 | HNO 3 | HNO 3 | HNO 3 | HNO 3 | HNO 3 | Malic acid | Malic acid | ||
| The pH of slurry | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 2.0 | 2.0 | ||
| The ORP of slurry (mV) | 980 | 980 | 980 | 980 | 980 | 980 | 1400 | 1400 | ||
| Polishing velocity (μ m/hr) | 0.8 | 0.4 | 0.3 | 0.4 | 0.9 | 0.4 | 1.1 | 2.5 | ||
| Surface assessment after the CMP | Surface roughness Ry (nm) | 30 | 5.8 | 5.2 | 4.0 | 6.1 | 6.2 | 8.5 | 9.2 | |
| Surface roughness Ra (nm) | 3.0 | 0.54 | 0.49 | 0.39 | 0.58 | 0.55 | 0.78 | 0.80 | ||
| Processed the thickness (nm) of the layer that influences | - | - | - | - | - | - | 300 | 100 | ||
| Remarks | ||||||||||
| The relative light output intensity of LED | 1.2 | 2.5 | 2.2 | 3.2 | 1.4 | 1.8 | - | 1.0 | ||
*DCIA-Na: DCCNa, TCIA: TCCA
*C.E.: comparative example, E.: example
As seeing from table 1 and table 2 are clear, by use in the surface-treated CMP technology that is used for element nitride crystal make by oxide and have at least-standard free energy of formation of the conversion of 850kJ/mol and be at least the abrasive particle of 4 Mohs' hardness, obtained to have the element nitride crystal substrate on the level and smooth and the second best in quality surface that is suitable for semiconductor device substrates.
Especially, to compare with the abrasive particle of comparative example 1, the abrasive particle of example 1 has at least-standard free energy of formation of the conversion of 850kJ/mol, its hardness is low simultaneously.Therefore, obtained higher polishing velocity and more level and smooth plane of crystal, and LED has the light output of higher relative intensity.In addition, compare with the abrasive particle of example 1, the abrasive particle of example 2 has lower hardness, causes somewhat low polishing velocity.Yet the standard free energy of formation of higher conversion provides the more level and smooth plane of crystal and the LED light output of higher relative intensity.
Example 14-22
Except will by HVPE growing n-type GaN crystal (adulterant: Si) section, similarly n type GaN crystalline substrates is carried out lappingout and CMP with example 2, so that form first type surface to have the oblique angle with respect to face as shown in table 3, therefore obtained the n type GaN crystalline substrates of 10mm * 10mm * thickness 0.5mm with high preferred orientation as shown in table 3.With these results being summarised in the table 3 with example 2.As for the oxidant of table 3, TCIA represents TCCA.
Table 3
| E.2 | E.14 | E.15 | E.16 | E.17 | E.18 | E.19 | E.20 | E.21 | E.22 | |||
| Substrate | The crystal plane orientation of first type surface | (0001) c-Ga face | (0001) c-Ga face | (0001) c-Ga face | (01-12) r-face | (10-11) s-face | (10-10) m-face | (11-22) | (11-21) | (11-20) a-face | (000-1) c-N face | |
| The oblique angle (°) | 0 | 2 | 5 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | ||
| C M P | Abrasive particle | The chemical species that comprises | Fe 2O 3 | Fe 2O 3 | Fe 2O 3 | Fe 2O 3 | Fe 2O 3 | Fe 2O 3 | Fe 2O 3 | Fe 2O 3 | Fe 2O 3 | Fe 2O 3 |
| Mohs' hardness | 6 | 6 | 6 | 6 | 6 | 6 | 6 | 6 | 6 | 6 | ||
| The standard free energy of formation (kJ/mol) of conversion | -570 | -570 | -570 | -570 | -570 | -570 | -570 | -570 | -570 | -570 | ||
| Granularity (μ m) | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 | ||
| Oxidant | TCIA | TCIA | TCIA | TCIA | TCIA | TCIA | TCIA | TCIA | TCIA | TCIA | ||
| Acid, alkali, salt (pH conditioning agent) | HCl | HCl | HCl | HCl | HCl | HCl | HCl | HCl | HCl | HCl | ||
| The pH of slurry | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | ||
| The ORP of slurry (mV) | 1450 | 1450 | 1450 | 1450 | 1450 | 1450 | 1450 | 1450 | 1450 | 1450 | ||
| Polishing velocity (μ m/hr) | 0.8 | 1.0 | 1.2 | 1.6 | 1.8 | 3.1 | 1.8 | 2.3 | 3.0 | 5.2 | ||
| Surface assessment after the CMP | Surface roughness Ry (nm) | 4.0 | 3.2 | 2.7 | 3.0 | 3.2 | 3.5 | 3.1 | 3.4 | 3.8 | 4.3 | |
| Surface roughness Ra (nm) | 0.42 | 0.34 | 0.28 | 0.31 | 0.33 | 0.35 | 0.32 | 0.35 | 0.36 | 0.41 | ||
| Processed the thickness (nm) of the layer that influences | - | - | - | - | - | - | - | - | - | |||
| Remarks | ||||||||||||
*TCIA: TCCA
*E.: example
As seeing from table 3 is clear, by the element nitride crystal substrate that has at the most 15 ° oblique angle is carried out CMP of the present invention, this angle is formed in { 0001} face, { 11-20} face, { 01-12} face, { 10-10} face, { 10-11} face, { the 11-21} face and { the element nitride crystal substrate with level and smooth and superior in quality surface has been made at the angle between the 11-22} face effectively arbitrarily of the first type surface of element nitride crystal substrate and wurtzite structure.
From relatively seeing between example 2,14 and 15, along with being increased to 2 ° and 5 ° with respect to the oblique angle of c-face from 0 °, polishing velocity uprises.In addition, from relatively seeing between example 2 and 16 to 22, the polishing velocity of CMP uprises in the following order: (000-1) face (the N atomic plane of c-face (the c-N face in the table 3))＞{ 10-10} face (m-face)＞{ 11-20} face (a-face)＞{ 11-21} face＞{ 11-22} face={ 10-11} face (s-face)＞{ 01-12} face (r-face)＞(0001) face (the Ga atomic plane of c-face).Think that the difference between the chemical stability between these faces can cause this result.
Example 23-29
For the n type GaN crystalline substrates after the CMP in the example 1, carried out utilizing the polyoxyalkylene alkyl (polyoxyalkylenealkylether of 0.15% mass ratio, be also referred to as POAAE hereinafter) the aqueous solution clean (cleaning) as neutral detergent with neutral the cleaning, utilization has 2N (normal concentration, normality) the KOH aqueous solution of concentration is as alkaline solution, or with the H with 0.5N (normal concentration) concentration
2SO
4The aqueous solution is as acid solution (with the polishing of acid solution or alkaline solution), and/or utilizes the pure water ultrasonic wave to clean and 1MHz (1 * 10
6Hz) ultrasonic wave.
Absorb the sponge and the artificial mobile sponge of neutral detergent on the surface of n type GaN crystalline substrates by extruding after the CMP, carried out utilizing the scouring of aforesaid neutral detergent.Scavenging period is 1 minute.
The following polishing.Particularly, being assemblied on the polissoir (not shown) and having on the surface plate 35 of 380mm diameter, placed polishing pad 38.When polishing fluid 37 when polishing fluid charging aperture 39 is provided to polishing pad 38, polishing pad 38 rotates around rotating shaft 35c.In addition, when weight 34 is placed on the crystal fixator 31 with GaN crystalline substrates (element nitride crystal 1) extruding during to polishing pad 38, n type GaN crystalline substrates (element nitride crystal 1) is around the rotating shaft 31c rotation of crystal fixator 31.In this mode, polished the surface ((c-face ((0001) face)) on the Ga atomic plane side) of n type GaN crystal.As polishing pad 38, used polyurethane suede (by the Supreme RN-R of Nitta Haas company manufacturing).As surface plate 35, used the stainless steel watch panel.Polish pressure is 19.6kPa (200gf/cm
2) to 49kPa (500gf/cm
2).Each all is 30 rev/mins to 100 rev/mins for the rotary speed of n type GaN crystalline substrates (III group-III nitride crystal 1) and polishing pad 38.Polishing time is 20 minutes.
Following having carried out cleaned with pure water.After CMP, be immersed in the pure water after will cleaning with neutral detergent or with the n type GaN crystalline substrates after alkaline solution or the acid solution polishing, and the ultrasonic wave of 1MHz is applied to pure water.Scavenging period is 20 minutes.
After cleaning, remain in the lip-deep impurity of n type GaN crystalline substrates, clean to polishing and/or with pure water by TXRF (always reflecting XRF) analysis and carry out elementary analysis with neutral detergent.In table 4, summarized this result.As for cleaning with neutral detergent in the table 4, POAAE represents polyoxyalkylene alkyl (polyoxyalkylenealkylether).
Table 4
| E.1 | E.23 | E.24 | E.25 | E.26 | E.27 | E.28 | E.29 | ||
| Process of surface treatment after the CMP | Clean (quality %) with neutral detergent | - | POAAE (0.15) | - | - | - | POAAE (0.15) | - | POAAE (0.15) |
| With acidity or alkaline solution polishing (N) | - | - | KOH (2) | H 2SO 4 (0.5) | - | - | Malic acid (1) | KOH (2) | |
| Clean with pure water | - | - | - | - | Ultrasonic wave | Ultrasonic wave | Ultrasonic wave | Ultrasonic wave | |
| Impurity level (* 10 on the plane of crystal 10atoms/cm 2) | Cr | 1800 | 400 | 700 | 300 | 600 | 150 | 200 | 0 |
| Si | 410 | 370 | 50 | 30 | 380 | 330 | 20 | 10 | |
| K | 110 | 90 | 10 | 30 | 20 | 15 | 0 | 0 | |
| S | 710 | 680 | 100 | 1100 | 280 | 220 | 40 | 30 | |
| |
630 | 410 | 220 | 160 | 380 | 280 | 100 | 50 | |
| Ca | 2500 | 2100 | 80 | 30 | 420 | 350 | 30 | 0 | |
*POAAE: polyoxyalkylene alkyl
*E.: example
As seeing from table 4 is clear, after CMP, the scouring by use neutral detergent, with alkaline solution or acid solution polishing with in the pure water cleaning at least one can reduce the lip-deep impurity of n type GaN crystalline substrates.In addition, by making up these cleanings or glossing, can further reduce the lip-deep impurity of n type GaN crystalline substrates.
Example 30-37, comparative example 7-9
The n type AlN crystal (adulterant: Si) cut into slices, to obtain the n type AlN crystalline substrates of diameter 40mm * thickness 0.5mm of HVPE method growth will be passed through along the face parallel with (0001) face.On the surface of n type AlN crystalline substrates (the c-face on the Ga atomic plane side, (0001) face), carried out and example 1 similar lappingout.Then, on the lappingout surface of n type AlN crystalline substrates, except use has the slurry of abrasive particle as shown in table 5, pH and ORP, similarly carried out CMP with example 1.Subsequently, utilize CMP n type AlN crystalline substrates afterwards, made semiconductor devices similarly with example 1.In table 5, summarized this result.
Table 5
| C.E. 7 | C.E. 8 | C.E. 9 | E.30 | E.31 | E.32 | E.33 | E.34 | E.35 | E.36 | E.37 | |||
| C M P | Abrasive particle | The chemical species that comprises | Al 2O 3 | ZrO 2 | CuO | Cr 2O 3 | Fe 2O 3 | Fe 3O 4 | NiO | ZnO | SnO 2 | Co 3O 4 | In 2O 3 |
| Mohs' hardness | 9 | 7 | 3.5 | 8.5 | 6 | 6 | 5.5 | 4 | 6.8 | 5 | 5 | ||
| The standard free energy of formation (kJ/mol) of conversion | -1130 | -920 | -340 | -770 | -570 | -580 | -500 | -720 | -600 | -470 | -700 | ||
| Granularity (μ m) | 0.5 | 0.2 | 1.0 | 0.5 | 1.2 | 1.0 | 1.0 | 2.0 | 1.0 | 1.0 | 2.0 | ||
| Oxidant | H 2O 2 | H 2O 2 | H 2O 2 | H 2O 2 | H 2O 2 | H 2O 2 | H 2O 2 | H 2O 2 | H 2O 2 | H 2O 2 | H 2O 2 | ||
| Acid, alkali, salt (pH conditioning agent) | HCl | HCl | HCl | HCl | HCl | HCl | HCl | HCl | HCl | HCl | HCl | ||
| The pH of slurry | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 | ||
| The ORP of slurry (mV) | 850 | 850 | 850 | 850 | 850 | 850 | 850 | 850 | 850 | 850 | 850 | ||
| Polishing velocity (μ m/hr) | 0.6 | 0.2 | 0 | 1.2 | 0.5 | 0.5 | 0.4 | 0.2 | 0.7 | 0.5 | 0.4 | ||
| Surface assessment after the CMP | Surface roughness Ry (nm) | 8.1 | 4.5 | 15 | 8.2 | 3.8 | 3.9 | 5.8 | 4.6 | 24 | 15 | 3.8 | |
| Surface roughness Ra (nm) | 0.75 | 0.41 | 1.1 | 0.81 | 0.39 | 0.39 | 0.49 | 0.42 | 2.2 | 1.2 | 0.36 | ||
| Processed the thickness (nm) of the layer that influences | 300 | 250 | 500 | 100 | - | - | - | - | - | - | - | ||
| Remarks | |||||||||||||
| The relative light output intensity of LED | - | - | - | 1.2 | 3.2 | 3.1 | 1.6 | 1.8 | 1.3 | 1.4 | 2.2 | ||
*C.E.: comparative example, E.: example
From the comparison between table 5 and table 1 and 2, be clear that, the surface treatment that is used for element nitride crystal of the present invention can provide the CMP of high polishing velocity, make when using n type AlN crystalline substrates, similar to the situation of using n type GaN crystalline substrates, also can obtain level and smooth and high-quality plane of crystal.In addition, as n type GaN crystalline substrates, n type AlN crystalline substrates has the higher light transmittance for short wavelength range, can obtain the LED of high light output thus.
Example 38
＜3-1〉lappingout of n type GaN crystalline substrates
Will be along the face parallel by the n type GaN crystal (adulterant: Si) cut into slices, of HVPE method growth to obtain the n type GaN crystalline substrates of diameter 30mm * thickness 0.5mm with (0001) face.On this n type GaN crystalline substrates, carried out and example 1 similar lappingout.After the lappingout, n type GaN crystalline substrates has that 500nm is thick, surface roughness Ry is 22nm and surface roughness Ra is the layer that being processed of 2.1nm influences.
＜3-2〉CMP of n type GaN plane of crystal
With reference to figure 2, the c-face on the N atomic plane side ((000-1) face) of the n type GaN crystalline substrates (element nitride crystal 1) after the lappingout is attached on the ceramic crystal fixator 21 with wax.Comprise abrasive particle 26 and be fixed to bonded-abrasive body 28 on the surface plate 25 that the diameter that is assemblied on the polissoir (not shown) is 300mm, rotate around rotating shaft 25c.In addition, weight 24 is placed on the crystal fixator 21 of fixing element nitride crystal 1, and this fixator is around its rotating shaft 21c rotation, and element nitride crystal 1 is pressed towards fixing abrasive particle body 28 simultaneously.In this mode, CMP is carried out on the surface (the c-face on the Ga atomic plane side, (0001) face) of n type GaN crystal.
By utilizing polyvinyl alcohol resin bond 27 to fix abrasive particle 26, this abrasive particle is the Cr with 0.5 μ m granularity
2O
3(Mohs' hardness: 8.5, the standard free energy of formation of conversion :-770kJ/mol) particulate, thus form fixing abrasive particle body 28.The content of abrasive particle is 15% mass ratio in fixing abrasive particle body 28.Polish pressure is 19.6kPa (200gf/cm
2) to 147kPa (1500gf/cm
2).Each all is 50 rev/mins to 400 rev/mins for the rotary speed of n type GaN crystalline substrates (element nitride crystal 1) and fixing abrasive particle body 28.Polishing time is 60 minutes.
CMP has 3.2 μ m/ hours high polishing velocity.After the CMP, n type GaN crystalline substrates has that 150nm is thick, surface roughness is that Ry is that 10nm and surface roughness Ra are the layer that being processed of 1.2nm influences.
＜3-3〉comprise the manufacturing of the semiconductor devices of n type GaN crystalline substrates
Similar with example 1, use CMP n type GaN crystalline substrates afterwards to make semiconductor devices.The result is summarized in the table 6.
Example 39-44, comparative example 10-14
Carry out lappingout and CMP, and, similarly make semiconductor devices with example 38 except using abrasive particle shown in the table 6 or 7 and the bond material for CMP.The result is summarized in table 6 and the table 7.In table 6 and table 7, represent phenolic resins as the bond material Ph that is used for CMP, PVA represents polyvinyl alcohol resin, and PI represents polyimide resin, and PA represents polyamide, and PE represents mylar.Refer to small resultant hole of breaking about " the fracture hole " of comparative example 13 as the plane of crystal that causes owing to the mechanical load among the CMP.Utilize the measurement of interference of light talysurf to resolve the degree of depth of ceasma.Many fractures hole has the 50nm or the above degree of depth.
Table 6
| C.E.10 | C.E.11 | C.E.12 | C.E.13 | C.E.14 | E.38 | E.39 | E.40 | |||
| C M P | Abrasive particle | The chemical species that comprises | Al 2O 3 | SiO 2 | CeO 2 | SiC | CuO | Cr 2O 3 | Fe 2O 3 | Fe 3O 4 |
| Mohs' hardness | 9 | 7 | 5 | 9.5 | 3.5 | 8.5 | 6 | 6 | ||
| The standard free energy of formation (kJ/mol) of conversion | -1130 | -920 | -1030 | - | -340 | -770 | -570 | -580 | ||
| Granularity (μ m) | 0.5 | 0.2 | 0.2 | 9.5 | 1.0 | 0.2 | 0.3 | 0.5 | ||
| The material that is used for bond | Ph | Ph | PVA | PI | PA | PVA | PVA | Ph | ||
| Polishing velocity (μ m/hr) | 1.5 | 0 | 0 | 2.0 | 0 | 3.2 | 1.1 | 0.9 | ||
| Surface after the CMP is estimated | Surface roughness Ry (nm) | 42 | 33 | 28 | 340 | 22 | 10 | 4.2 | 4.1 | |
| Surface roughness Ra (nm) | 3.9 | 3.1 | 2.4 | 22 | 2.0 | 1.2 | 0.36 | 0.35 | ||
| Processed the thickness (nm) of the layer that influences | 400 | 500 | 500 | 1200 | 500 | 150 | 50 | 50 | ||
| Remarks | The fracture hole | |||||||||
| The relative light output intensity of LED | - | - | - | - | - | 0.8 | 1.5 | 1.5 | ||
*Ph: phenolic resins, PVA: polyvinyl resin, PI: polyimide resin, PA: polyamide
*C.E.: comparative example, E.: example
Table 7
| E.41 | E.42 | E.43 | E.44 | ||||
| C M P | Abrasive particle | The chemical species that comprises | NiO | SnO 2 | Co 3O 4 | Ga 2O 3 | |
| Mohs' hardness | 5.5 | 6.8 | 5 | 5 | |||
| The standard free energy of formation (kJ/mol) of conversion | -500 | -600 | -470 | -740 | |||
| Granularity (μ m) | 1.0 | 1.0 | 1.0 | 1.0 | |||
| The material that is used for bond | PE | PE | PI | PVA | |||
| Polishing velocity (μ m/hr) | 0.8 | 1.2 | 1.0 | 0.8 | |||
| Surface after the CMP is estimated | Surface roughness Ry (nm) | 7.2 | 39 | 28 | 7.5 | ||
| Surface roughness Ra (nm) | 0.65 | 3.3 | 2.5 | 0.82 | |||
| Processed the thickness (nm) of the layer that influences | 50 | 50 | 50 | 50 | |||
| Remarks | |||||||
| The relative light output intensity of LED | 1.4 | 1.2 | 1.2 | 1.3 | |||
*PE: mylar, PI: polyimide resin, PVA: polyvinyl alcohol resin
*E.: example
As seeing from table 6 and table 7 are clear, for the dry method CMP of the surface treatment method of element nitride crystal, can use make by oxide and have at least-standard free energy of formation of 850kJ/mol conversion and Mohs' hardness be at least the element nitride crystal substrate that 4 abrasive particle obtains to have the level and smooth and high-quality surface that is suitable for semiconductor device substrates.
Although described with example the present invention in detail, understand that clearly it only is exemplary and example, rather than restrictive, the spirit and scope of the present invention are only by appended claim restriction.
Claims (16)
1. the surface treatment method on the surface of chemistry and machine glazed finish element nitride crystal (1),
Use the abrasive particle (16,26) of oxide,
Described abrasive particle (16,26) has at least-standard free energy of formation of 850kJ/mol as the conversion value of per 1 mole oxygen molecule and
Described abrasive particle (16,26) has and is at least 4 Mohs' hardness.
2. according to the surface treatment method of claim 1, wherein
Described abrasive particle (16) be dispersed in the solvent with as slurry (17) and
The pH value x of described slurry (17) and Eo+ value y (mV) satisfy relation (i) and (ii):
Y 〉=-50x+1000 ... (i); With
y≤-50x+1900 ...(ii)。
3. according to the surface treatment method of claim 1, wherein
Described slurry (1 7) has and is at most 5 or be at least 9 pH.
4. according to the surface treatment method of claim 1, wherein
Described abrasive particle (16,26) is to comprise to be selected from by Fe
2O
3, Fe
3O
4, NiO, ZnO, CoO, Co
3O
4, GeO
2, Ga
2O
3, In
2O
3, Cr
2O
3And SnO
2The abrasive particle of at least a chemical species in the group of forming.
5. according to the surface treatment method of claim 1, wherein
Utilize neutral detergent to clean the described surface of the element nitride crystal (1) of chemistry and machine glazed finish.
6. according to the surface treatment method of claim 1, wherein
Utilize the described surface of the element nitride crystal (1) of alkaline solution or acid solution polishing chemistry and machine glazed finish.
7. according to the surface treatment method of claim 1, wherein
Clean the described surface of the element nitride crystal (1) of chemistry and machine glazed finish with pure water.
8. according to the surface treatment method of claim 1, wherein
The described surface of element nitride crystal (1) stood to grind or lappingout before by chemistry and machine glazed finish.
9. one kind by carrying out the element nitride crystal substrate (610) of the chemistry and the surface treatment of machine glazed finish acquisition to the surface of element nitride crystal (1),
Described surface treatment utilizes the abrasive particle (16,26) of oxide, and described abrasive particle (16,26) has at least-standard free energy of formation of 850kJ/mol is as the conversion value of per 1 mole oxygen molecule, and described abrasive particle (16,26) has and is at least 4 Mohs' hardness.
10. according to the element nitride crystal substrate of claim 9, wherein
Described element nitride crystal substrate has the surface roughness Ry of 30nm at the most.
11. according to the element nitride crystal substrate of claim 9, wherein
Described element nitride crystal substrate has the surface roughness Ra of 3nm at the most.
12. according to the element nitride crystal substrate of claim 9, wherein
By the first type surface of described element nitride crystal substrate (610) and wurtzite structure { 0001} face, { 11-20} face, { 01-12} face, { 10-10} face, { 10-11} face, { 11-21} face and { oblique angle that the 11-22} face forms is at most 15 ° arbitrarily.
13. the element nitride crystal substrate with epitaxial loayer comprises the III group iii nitride layer (650) of the one deck at least that forms by epitaxial growth at least one first type surface of element nitride crystal substrate as claimed in claim 9 (610).
14. a semiconductor devices comprises element nitride crystal substrate as claimed in claim 9 (610) and is formed on the III group iii nitride layer (650) of the one deck at least at least one first type surface of described element nitride crystal substrate.
15. manufacture method with element nitride crystal substrate of epitaxial loayer, wherein select element nitride crystal substrate as claimed in claim 9 (610) as substrate, and the III group iii nitride layer (650) of one deck at least of at least one first type surface of described element nitride crystal substrate (610), growing.
16. the manufacture method of a semiconductor devices is wherein selected element nitride crystal substrate as claimed in claim 9 (610) the III group iii nitride layer (650) of one deck at least of growing as substrate and at least one first type surface of described element nitride crystal substrate (610).
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| JPS6165439A (en) * | 1984-09-06 | 1986-04-04 | Sumitomo Electric Ind Ltd | Manufacture of stepped wafer |
| JP2000315666A (en) * | 1999-04-28 | 2000-11-14 | Hitachi Ltd | Manufacture of semiconductor integrated circuit device |
| JP2004072099A (en) * | 2003-08-01 | 2004-03-04 | Hitachi Ltd | Polishing method |
| JP2005183738A (en) * | 2003-12-19 | 2005-07-07 | Sharp Corp | Method and apparatus for chemomechanical polishing |
| JP4752214B2 (en) * | 2004-08-20 | 2011-08-17 | 住友電気工業株式会社 | Surface treatment method of AlN crystal for epitaxial layer formation |
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