CN100594625C - Gallium nitride based LED chip and fabricating method thereof - Google Patents
Gallium nitride based LED chip and fabricating method thereof Download PDFInfo
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- CN100594625C CN100594625C CN200710177273A CN200710177273A CN100594625C CN 100594625 C CN100594625 C CN 100594625C CN 200710177273 A CN200710177273 A CN 200710177273A CN 200710177273 A CN200710177273 A CN 200710177273A CN 100594625 C CN100594625 C CN 100594625C
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Abstract
The invention relates to a gallium nitride based light-emitting diode chip and a method for manufacturing the same. The method comprises the following steps: planning a crystal grain area and a cutting path area on the surface of an epitaxial slice; removing a protective mask of the cutting path area and then removing an undeveloped photoresist; performing dry etching on the cutting path area to expose N-type gallium nitride and form a side wall, wherein the distance between the surface of the N-type gallium nitride and the surface of a substrate of the epitaxial slice is between 1 and 1.5mu m; performing wet etching on the side wall and the surface of the N-type gallium nitride in an alkaline solution so as to form a roughened side wall of the N-type gallium nitride and a roughened surface of the N-type gallium nitride; and performing dry etching on the surface of the N-type gallium nitride, making use of the lattice defect formed in the process of epitaxy to form a nanometer columnarstructure on the surface of the N-type gallium nitride, and finally manufacturing the chip. The chip can improve the external luminous efficiency of the gallium nitride based light-emitting diode chip.
Description
Technical field
The invention belongs to the gallium nitride based light emitting diode technical field, particularly a kind of gallium nitride LED chip and preparation method thereof.
Background technology
Semiconductor light-emitting-diode is used increasingly extensive, the trend that replaces incandescent lamp and fluorescent lamp is particularly arranged aspect illumination, but also face some technical problems at present, particularly light taking-up efficient is lower, usually influence light and take out the reason that efficient mainly contains three aspects: a kind of is owing to the absorption of material to light, another kind is that light produces total reflection when passing different medium, and also having a kind of is the Fresnel effect loss of light.
Conventional at present technology of making light-emitting diode chip for backlight unit is, epitaxial growth obtains light-emitting diode structure successively on substrate 1, N type GaN layer 2, active layer 3, P type GaN layer 4 obtains the Cutting Road of chip and surface 5 and the sidewall 6 of N type GaN by etching method, make transparency conducting layer 7 then, and forming P type Ohmic electrode 8, N type Ohmic electrode 9, the method with scribing or cutting is divided into single crystal grain at last, also promptly obtains single chip.As shown in Figure 1, the index path of the light-emitting diode chip for backlight unit that is made into for common process, because N type GaN refraction coefficient is bigger, its critical angle has only about 23 °, therefore only the lateral light of some can directly penetrate, most lateral light forms total reflection and loses at chip internal, thereby causes the external light emission efficiency of chip lower.
Summary of the invention
In view of this, in order to solve the low problem of gallium nitride LED chip external light emission efficiency that exists in the prior art, main purpose of the present invention is to provide a kind of gallium nitride LED chip and preparation method thereof, by reducing the total reflection of light-emitting diode chip for backlight unit inside, increase the taking-up of lateral light, thereby promote the external light emission efficiency of light-emitting diode chip for backlight unit.
For achieving the above object, technical scheme of the present invention is achieved in that
A kind of gallium nitride LED chip, include epitaxial wafer, nesa coating, P type Ohmic electrode and N type Ohmic electrode, described epitaxial wafer is made up of substrate, n type gallium nitride layer, active layer and P type gallium nitride layer, described n type gallium nitride layer has surface and the sidewall that is exposed and is step-like, wherein, this n type gallium nitride layer is exposed and the surface of contiguous described substrate is the nanometer column structure, and the sidewall of the n type gallium nitride layer that is connected with this surface is the sidewall of alligatoring.
Make the method for above-mentioned gallium nitride LED chip, comprise the steps:
A, generate earlier the protection mask, coat photoresist again,, cook up the figure of grained region and the figure in Cutting Road zone then at the photoresist photomask surface and develop on the surface of gallium nitride based LED epitaxial slice;
The protection mask in b, removal Cutting Road zone, and remove undeveloped photoresist;
C, pressure more than or equal to 5 millitorrs and condition smaller or equal to 10 millitorrs under, dry ecthing is carried out in the Cutting Road zone, exposes n type gallium nitride and form sidewall, and the distance of the surface of n type gallium nitride and substrate surface is more than or equal to 1 μ m and smaller or equal to 1.5 μ m;
The time is carried out more than or equal to 30min and smaller or equal to the wet etching of 70min in d, oppose side wall and n type gallium nitride surface in alkaline solution, form the n type gallium nitride sidewall of alligatoring and the n type gallium nitride surface of alligatoring;
E, pressure more than or equal to 5 millitorrs and condition smaller or equal to 30 millitorrs under, dry ecthing is carried out on the n type gallium nitride surface, the lattice defect that forms in n type gallium nitride and the substrate brilliant process of heap of stone when utilizing epitaxial growth makes the surface of n type gallium nitride form the nanometer column structure;
The protection mask on f, removal grained region surface; then from P type gallium nitride surface down dry ecthing expose the n type gallium nitride layer; form nesa coating at P type gallium nitride surface again; further prepare P type Ohmic electrode; at last do not pass through the surface preparation N type Ohmic electrode of the n type gallium nitride of roughening treatment, form gallium nitride LED chip at this.
Wherein:
The time of wet etching is more than or equal to 50min and smaller or equal to 70min in the steps d;
The degree of depth of dry ecthing is more than or equal to 0.1 μ m and smaller or equal to 1.0 μ m among the step e;
Pressure among the step e is more than or equal to 15 millitorrs and smaller or equal to 30 millitorrs;
The r.m.s. roughness of n type gallium nitride alligatoring sidewall is more than or equal to 2.7nm and smaller or equal to 8.2nm in the described steps d;
The r.m.s. roughness of n type gallium nitride coarse surface is more than or equal to 3.6nm and smaller or equal to 13.2nm in the steps d;
The width of dry ecthing is more than or equal to 10 μ m and smaller or equal to 30 μ m among the step c.
Compared with prior art, the present invention adopts dry etching technology etching Cutting Road earlier, soak this epitaxial wafer with alkaline solution again, utilize the anisotropic etching characteristic of wet etching to reach the purpose on alligatoring sidewall and N type GaN surface, reduce the total reflection of light-emitting diode chip for backlight unit inside simultaneously, and increase the taking-up of lateral light.In addition, epitaxial wafer because the characteristic of backing material and GaN does not match, forms some lattice defects easily in brilliant process of heap of stone in epitaxial process usually, and many more near the substrate lattice defective more.Behind the Cutting Road of dry ecthing for the first time, N type GaN layer after the dry ecthing, can make these lattice defects display near backing material once more, thereby form the coarse surface with nanometer column structure, this coarse surface further reduces the total reflection of light-emitting diode chip for backlight unit inside.The present invention has increased light and has taken out efficient by the method that dry ecthing combines with wet etching, has finally promoted the external light emission efficiency of light-emitting diode chip for backlight unit.
Description of drawings
The index path of the light-emitting diode chip for backlight unit that Fig. 1 is made into for common process;
Fig. 2 is the structural representation of LED epitaxial slice;
Fig. 3 is the making flow chart of light-emitting diode chip for backlight unit of the present invention;
Fig. 4 finishes photoetching and the vertical view behind the wet etching for the first time for epitaxial wafer of the present invention;
Fig. 5 is the structural representation after the single crystal grain of epitaxial wafer of the present invention is finished dry ecthing for the first time;
Fig. 6 is the structural representation after the single crystal grain of epitaxial wafer of the present invention is finished the wet etching second time;
Fig. 7 is the structural representation after the single crystal grain of epitaxial wafer of the present invention is finished dry ecthing for the second time;
Fig. 8 is the electron scanning micrograph of 80000 times the local nanometer column structure of N type GaN for multiplication factor;
Fig. 9 is the structural representation of gallium nitride LED chip of the present invention;
Figure 10 is the structural representation of gallium nitride LED chip of the present invention.
Embodiment
Embodiment 1
One GaN based LED epitaxial slice is provided, and as shown in Figure 2, the structure of epitaxial wafer comprises Sapphire Substrate 11, N type GaN layer 12, active layer 13, P type GaN layer 14.The material of substrate also can be carborundum, zinc sulphide or GaAs except sapphire.
Please refer to Fig. 3, the manufacture method of gallium nitride LED chip of the present invention comprises the steps:
A, generate earlier protection mask 15, coat photoresist again, then utilize lithography mask version at the photoresist photomask surface and develop, cook up the figure of grained region and the figure in Cutting Road zone 16 on the surface of epitaxial wafer;
B, wet etching is carried out in Cutting Road zone 16, the protection mask 15 in Cutting Road zone 16 is removed in etching, removes undeveloped photoresist at last, exposes the protection mask 15 on grained region surface, as shown in Figure 4;
C, under the pressure environment of 5 millitorrs, utilize the plasma etching board mainly dry ecthing to be carried out in Cutting Road zone 16 in the mode of chemical etching, expose N type GaN layer 12 and form sidewall, and the surface 18 of the N type GaN after the dry ecthing is 1.5 μ m with the distance on the surface of Sapphire Substrate 11, etched width is 10 μ m, as shown in Figure 5, this etched width is relevant with the crystallite dimension size of design;
D, wet etching 50min is carried out on oppose side wall and N type GaN surface 18 in alkaline solution, the sidewall of the reaction pair N type GaN of alkaline solution and N type GaN and surface energy produce certain alligatoring effect, the isotropic etching characteristic oppose side wall of wet etching and N type GaN surface 18 produce the alligatoring effect, form the N type GaN sidewall 17 of alligatoring and 18 (as shown in Figure 6) of N type GaN surface of alligatoring, the r.m.s. roughness of N type GaN sidewall 17 is 2.7nm, the r.m.s. roughness on N type GaN surface 18 is 3.6nm, and the N type GaN sidewall 17 and the surface 18 of this alligatoring can provide more outgoing chance to light by the total reflection that reduces gallium nitride LED chip inside;
E, under the pressure environment of 5 millitorrs, utilize the plasma etching board mainly dry ecthing to be carried out on the N type GaN surface 18 of finishing the alligatoring effect in the mode of physical shock, etched depth is 1 μ m, the degree of depth of dry ecthing is relevant with the epitaxial structure of epitaxial wafer, utilize the lattice defect that forms in N type GaN12 and the Sapphire Substrate 11 brilliant processes of heap of stone, thereby make the surface 18 of N type GaN form nanometer column structure (as shown in Figure 7), further strengthened the alligatoring effect on surface 18.Fig. 8 is to be the photo of 80000 times nanometer column structure by the observed multiplication factor of scanning electron microscopy (SEM), this nanometer column structure has awl post height, the coarse surface that density is big has further reduced the total reflection of gallium nitride LED chip inside;
The protection mask on f, removal grained region surface; following from P type GaN14 surface down, the step of dry ecthing one appropriate depth exposes N type GaN layer 12; form nesa coating 19 on P type GaN14 surface again; further preparation P type Ohmic electrode 20; at last do not pass through the surface preparation N type Ohmic electrode 21 of the N type GaN12 of roughening treatment, form the high-brightness GaN-based light-emitting diode chip at this.
The manufacture method of gallium nitride LED chip of the present invention comprises the steps:
A, generate earlier protection mask 15, coat photoresist again, then utilize lithography mask version at the photoresist photomask surface and develop, cook up the figure of grained region and the figure in Cutting Road zone 16 on the surface of epitaxial wafer;
B, wet etching is carried out in Cutting Road zone 16, the protection mask 15 in Cutting Road zone 16 is removed in etching, removes undeveloped photoresist at last, exposes the protection mask 15 on grained region surface;
C, under the pressure environment of 10 millitorrs, utilize the plasma etching board mainly dry ecthing to be carried out in Cutting Road zone 16 in the mode of chemical etching, expose N type GaN layer 12 and form sidewall, and the surface 18 of the N type GaN after the dry ecthing is 1 μ m with the distance on Sapphire Substrate 11 surfaces, etched width is 30 μ m, and this etched width is relevant with the crystallite dimension size of design;
D, wet etching 70min is carried out on oppose side wall and N type GaN surface 18 in alkaline solution, the sidewall of the reaction pair N type GaN12 of alkaline solution and N type GaN12 and surface energy produce certain alligatoring effect, the isotropic etching characteristic oppose side wall of wet etching and N type GaN surface 18 produce the alligatoring effect, form the N type GaN sidewall 17 of alligatoring and the N type GaN surface 18 of alligatoring, the r.m.s. roughness of N type GaN sidewall 17 is 8.2nm, and the r.m.s. roughness on N type GaN surface 18 is 13.2nm;
E, under the pressure environment of 15 millitorrs, utilize the plasma etching board mainly dry ecthing to be carried out on the N type GaN surface 18 of finishing the alligatoring effect in the mode of physical shock, etched depth is 0.8 μ m, utilize the lattice defect that forms in N type GaN12 and the Sapphire Substrate 11 brilliant processes of heap of stone, thereby make the surface 18 of N type GaN form the nanometer column structure;
The protection mask on f, removal grained region surface; following from P type GaN14 surface down, the step of dry ecthing one appropriate depth exposes N type GaN layer 12; form nesa coating 19 on P type GaN14 surface again; further preparation P type Ohmic electrode 20; at last do not pass through the surface preparation N type Ohmic electrode 21 of the N type GaN12 of roughening treatment, form the high-brightness GaN-based light-emitting diode chip at this.
The manufacture method of gallium nitride LED chip of the present invention comprises the steps:
A, generate earlier protection mask 15, coat photoresist again, then utilize lithography mask version at the photoresist photomask surface and develop, cook up the figure of grained region and the figure in Cutting Road zone 16 on the surface of epitaxial wafer;
B, wet etching is carried out in Cutting Road zone 16, the protection mask 15 in Cutting Road zone 16 is removed in etching, removes undeveloped photoresist at last, exposes the protection mask 15 on grained region surface;
C, under the pressure environment of 7 millitorrs, utilize the plasma etching board mainly dry ecthing to be carried out in Cutting Road zone 16 in the mode of chemical etching, expose N type GaN layer 12 and form sidewall, and the surface 18 of the N type GaN after the dry ecthing is 1.2 μ m with the distance on Sapphire Substrate 11 surfaces, etched width is 20 μ m, and this etched width is relevant with the crystallite dimension size of design;
D, wet etching 60min is carried out on oppose side wall and N type GaN surface 18 in alkaline solution, the sidewall of the reaction pair N type GaN12 of alkaline solution and N type GaN12 and surface energy produce certain alligatoring effect, the isotropic etching characteristic oppose side wall of wet etching and N type GaN surface 18 produce the alligatoring effect, form the N type GaN sidewall 17 of alligatoring and the N type GaN surface 18 of alligatoring, the r.m.s. roughness of N type GaN sidewall 17 is 4.8nm, and the r.m.s. roughness on N type GaN surface 18 is 9.6nm;
E, under the pressure environment of 30 millitorrs, utilize the plasma etching board mainly dry ecthing to be carried out on the N type GaN surface 18 of finishing the alligatoring effect in the mode of physical shock, etched depth is 0.1 μ m, utilize the lattice defect that forms in N type GaN12 and the Sapphire Substrate 11 brilliant processes of heap of stone, thereby make the surface 18 of N type GaN form the nanometer column structure;
The protection mask on f, removal grained region surface; following from P type GaN14 surface down, the step of dry ecthing one appropriate depth exposes N type GaN layer 12; form nesa coating 19 on P type GaN14 surface again; further preparation P type Ohmic electrode 20; at last do not pass through the surface preparation N type Ohmic electrode 21 of the N type GaN12 of roughening treatment, form the high-brightness GaN-based light-emitting diode chip at this.
Embodiment 4
The manufacture method of gallium nitride LED chip of the present invention comprises the steps:
A, generate earlier protection mask 15, coat photoresist again, then utilize lithography mask version at the photoresist photomask surface and develop, cook up the figure of grained region and the figure in Cutting Road zone 16 on the surface of epitaxial wafer;
B, wet etching is carried out in Cutting Road zone 16, the protection mask 15 in Cutting Road zone 16 is removed in etching, removes undeveloped photoresist at last, exposes the protection mask 15 on grained region surface;
C, under the pressure environment of 9 millitorrs, utilize the plasma etching board mainly dry ecthing to be carried out in Cutting Road zone 16 in the mode of chemical etching, expose N type GaN layer 12 and form sidewall, and the surface 18 of the N type GaN after the dry ecthing is 1.4 μ m with the distance on Sapphire Substrate 11 surfaces, etched width is 30 μ m, and this etched width is relevant with the crystallite dimension size of design;
D, wet etching 65min is carried out on oppose side wall and N type GaN surface 18 in alkaline solution, the sidewall of the reaction pair N type GaN12 of alkaline solution and N type GaN12 and surface energy produce certain alligatoring effect, the isotropic etching characteristic oppose side wall of wet etching and N type GaN surface 18 produce the alligatoring effect, form the N type GaN sidewall 17 of alligatoring and the N type GaN surface 18 of alligatoring, the r.m.s. roughness of N type GaN sidewall 17 is 5.7nm, and the r.m.s. roughness on N type GaN surface 18 is 10.8nm;
E, under the pressure environment of 20 millitorrs, utilize the plasma etching board mainly dry ecthing to be carried out on the N type GaN surface 18 of finishing the alligatoring effect in the mode of physical shock, etched depth is 0.7 μ m, utilize the lattice defect that forms in N type GaN12 and the Sapphire Substrate 11 brilliant processes of heap of stone, thereby make the surface 18 of N type GaN form the nanometer column structure;
The protection mask on f, removal grained region surface; following from P type GaN14 surface down, the step of dry ecthing one appropriate depth exposes N type GaN layer 12; form nesa coating 19 on P type GaN14 surface again; further preparation P type Ohmic electrode 20; at last do not pass through the surface preparation N type Ohmic electrode 21 of the N type GaN12 of roughening treatment, form the high-brightness GaN-based light-emitting diode chip at this.
In wet etch step, can adopt other ancillary methods, utilizing increases molecular motion, thereby improves the principle of reaction rate, and shortens the time of wet etching, can reach the identical alligatoring sidewall and the effect on surface.
For example:
Embodiment 5
Other conditions are constant, change the time of the wet etching of steps d among the embodiment 2 into 30min, simultaneously heat this alkaline solution with 80 ℃ temperature, increase the motion of molecule by heating, thereby improve the reaction rate of N type GaN and alkaline solution, shorten the time of wet etching, and reach identical alligatoring effect.
Embodiment 6
Other conditions are constant, change the time of the wet etching of steps d among the embodiment 4 into 40min, be this alkaline solution of supersonic oscillations of 28KHz/s with the frequency simultaneously, increase the motion of molecule by supersonic oscillations, thereby improve the reaction rate of N type GaN and alkaline solution, shorten the time of wet etching, and reach identical alligatoring effect.
In an embodiment of the present invention, dry ecthing all is to adopt the plasma etching board in low pressure (below 50 millitorrs) operation down, but also can adopt other equipment in high pressure (about 400 millitorrs) operation down.
As shown in Figure 9, be the structural representation of gallium nitride LED chip of the present invention.Gallium nitride LED chip of the present invention comprises surface 18 and the sidewall 17 of the N type GaN that is exposed, and the surface 18 of this N type GaN is the nanometer column structure, and the sidewall 17 of N type GaN is the sidewall of alligatoring.
As shown in figure 10, index path for gallium nitride LED chip of the present invention, the nanometer column structure on the alligatoring sidewall 17 of N type GaN of the present invention and N type GaN surface 18 can make light enter more in the critical angle and provide more outgoing chance to light, thereby improves the external light emission efficiency of light-emitting diode chip for backlight unit.
Table 1 is after the chip of the employing embodiment of the invention 1 to embodiment 6 is packaged into green light LED, the luminous flux when injection current is 350mA, and the size of chip is 1000 μ m * 1000 μ m, i.e. 40mil * 40mil.
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | The mean value of luminous flux |
| Luminous flux (lumen) | 32.3 | 34.4 | 32.7 | 33.5 | 33.9 | 33.1 | 33.32 |
Table 1
Comparison by data in the table 1, can find, the mean value that adopts the present invention to make the luminous flux of the light-emitting diode that obtains is 33.32 lumens, and the mean value that the same terms adopts common process to make the luminous flux of the light-emitting diode that obtains down only is about 25.94 lumens, therefore, under comparing, the luminous flux of the light-emitting diode that the present invention makes has promoted about 28.45%.
The above is preferred embodiment of the present invention only, is not to be used to limit protection scope of the present invention.
Claims (8)
1, a kind of gallium nitride LED chip, include epitaxial wafer, nesa coating, P type Ohmic electrode and N type Ohmic electrode, described epitaxial wafer is made up of substrate, n type gallium nitride layer, active layer and P type gallium nitride layer, described n type gallium nitride layer has surface and the sidewall that is exposed and is step-like, it is characterized in that, described n type gallium nitride layer is exposed and the surface of contiguous described substrate is the nanometer column structure, and the sidewall of the n type gallium nitride layer that is connected with this surface is the sidewall of alligatoring.
2, a kind of method of making the gallium nitride LED chip of claim 1 is characterized in that, this method comprises the steps:
A, generate earlier the protection mask, coat photoresist again,, cook up the figure of grained region and the figure in Cutting Road zone then at the photoresist photomask surface and develop on the surface of gallium nitride based LED epitaxial slice;
The protection mask in b, removal Cutting Road zone, and remove undeveloped photoresist;
C, pressure more than or equal to 5 millitorrs and condition smaller or equal to 10 millitorrs under, dry ecthing is carried out in the Cutting Road zone, exposes n type gallium nitride and form sidewall, and the distance of the surface of n type gallium nitride and substrate surface is more than or equal to 1 μ m and smaller or equal to 1.5 μ m;
The time is carried out more than or equal to 30min and smaller or equal to the wet etching of 70min in d, oppose side wall and n type gallium nitride surface in alkaline solution, form the n type gallium nitride sidewall of alligatoring and the n type gallium nitride surface of alligatoring;
E, pressure more than or equal to 5 millitorrs and condition smaller or equal to 30 millitorrs under, dry ecthing is carried out on the n type gallium nitride surface, the lattice defect that forms in n type gallium nitride and the substrate brilliant process of heap of stone when utilizing epitaxial growth makes the surface of n type gallium nitride form the nanometer column structure;
The protection mask on f, removal grained region surface; then from P type gallium nitride surface down dry ecthing expose the n type gallium nitride layer; form nesa coating at P type gallium nitride surface again; further prepare P type Ohmic electrode; at last do not pass through the surface preparation N type Ohmic electrode of the n type gallium nitride of roughening treatment, form gallium nitride LED chip at this.
3, the method for making gallium nitride LED chip according to claim 2 is characterized in that, the time of wet etching is more than or equal to 50min and smaller or equal to 70min in the described steps d.
4, the method for making gallium nitride LED chip according to claim 3 is characterized in that, the degree of depth of dry ecthing is more than or equal to 0.1 μ m and smaller or equal to 1.0 μ m among the described step e.
5, the method for making gallium nitride LED chip according to claim 4 is characterized in that, the pressure among the described step e is more than or equal to 15 millitorrs and smaller or equal to 30 millitorrs.
6, the method for making gallium nitride LED chip according to claim 5 is characterized in that, the r.m.s. roughness of n type gallium nitride alligatoring sidewall is more than or equal to 2.7nm and smaller or equal to 8.2nm in the described steps d.
7, the method for making gallium nitride LED chip according to claim 6 is characterized in that, the r.m.s. roughness of n type gallium nitride coarse surface is more than or equal to 3.6nm and smaller or equal to 13.2nm in the described steps d.
According to the method for claim 2,3,4,5,6 or 7 described making gallium nitride LED chips, it is characterized in that 8, the width of dry ecthing is more than or equal to 10 μ m and smaller or equal to 30 μ m among the described step c.
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| CN101807644A (en) * | 2010-03-05 | 2010-08-18 | 厦门大学 | Preparation method of GaN-based light emitting diode (LED) with high light emitting efficiency |
| CN101882659A (en) * | 2010-06-28 | 2010-11-10 | 亚威朗光电(中国)有限公司 | Light-emitting diode chip and method for manufacturing same |
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