The inhomogeneity method of a kind of raising Sapphire Substrate epitaxial layer of gallium nitride
Technical field
The present invention relates to the inhomogeneity method of growing GaN epitaxial loayer on a kind of raising sapphire pattern substrate, belong to the photoelectron technology field.
Background technology
For GaN based light-emitting diode (GaN-LED), the warpage issues of backing material and the uniformity of grown epitaxial layer are the objects that numerous people pay close attention to; Backing material at present commonly used has sapphire, Si, SiC.Usually, the epitaxial loayer of GaN sill and device mainly is grown on the Sapphire Substrate, and Sapphire Substrate has many advantages: at first, the production technology of Sapphire Substrate is ripe, device quality is better; Secondly, sapphire stability is fine, is fit in the high growth temperature environment; The 3rd, sapphire mechanical strength is high, is easy to process and clean.Therefore, mostly all prepare GaN base LED with sapphire as substrate.But use sapphire also to have some problems as substrate, because lattice mismatch and thermal stress mismatch, the warpage of substrate own is apparent in view, and epitaxial loayer easily splits behind the growing GaN, affects the making of chip, causes difficulty for follow-up device fabrication.
Lattice mismatch and thermal stress mismatch problems for Sapphire Substrate, adopt at present sapphire pattern substrate technology (PSS) more, PSS can solve owing to having larger lattice mismatch and coefficient of thermal expansion mismatch between sapphire and the GaN on the one hand, take a face as example, Sapphire Substrate lattice constant 3.18, thermal coefficient of expansion 7.5 * 10
-6K
-1, GaN lattice constant 0.47, thermal coefficient of expansion 5.59 * 10
-6K
-1The simultaneously miniature figure structural change of PSS the growth course of GaN, can suppress defective and extend to epitaxial surface, reduced the defect concentration of extension.On the other hand, there are gap in the refractive index of extension GaN and Sapphire Substrate and the refractive index of air, the refractive index 2.4 of GaN material is higher than the refractive index 1.0 of Sapphire Substrate refractive index 1.7 and air, the light that sends from the GaN active area arrives Sapphire Substrate, when incidence angle during greater than critical angle, total reflection namely occurs, propagate through the GaN material, interface to GaN and air, the GaN refractive index is also greater than the refractive index of air, when incidence angle during greater than critical angle, equally total reflection phenomenon can occur, multiple total reflection causes light that the GaN active area sends to be absorbed by material through refraction repeatedly between sapphire and air like this, has reduced the extraction efficiency of light, the PSS graphic structure has changed the round that active area sends light, reduce incidence angle, reduced the chance of total reflection, increased the bright dipping chance, more light is reflected through the PSS structure function, improved light extraction efficiency.Although the PSS technology has improved light extraction efficiency, but do not reduce the stress that produces in the growth course, the uniformity of grown epitaxial layer is also failed so is increased.
Chinese patent file CN1294649 discloses a kind of method of wet etching sapphire pattern substrate, comprise: steam coating silicon dioxide mask layer on sapphire C face is carved into bar shaped by photoetching technique, then this substrate of corrosive liquid wet etching, remove at last mask, obtain sapphire pattern substrate.Adopt the substrate grown epitaxial layer that directly forms figure, during the growing GaN base, the threading dislocation direction is by vertically transferring level to, thereby reduces GaN base epitaxial loayer dislocation density, raising epitaxial loayer crystal mass.But the method can not discharge stress in advance, produces larger stress in the GaN growth course, makes it warpage, and the uniformity of epitaxial wafer is also poor after the growth.In addition, use wet etching to obtain the mask pattern of silicon dioxide, because third dimension (size) is very little, the method for wet etching is difficult to the size of control figure, and the cost of dry etching is very high, is unfavorable for mass production.
Summary of the invention
The present invention is directed to the problem that prior art exists, a kind of raising sapphire flat substrate or the inhomogeneity method of graph substrate epitaxial layer of gallium nitride are provided.
Terminological interpretation:
MOCVD: metal organic vapor phase epitaxy.
The GaN-LED:GaN based light-emitting diode.
PSS figure: Patterned sapphire substrate sapphire pattern substrate.
Wet etching: be that the etching material is immersed in the technology of corroding in the corrosive liquid.The mixed solution of this area sulfuric acid commonly used and phosphoric acid corrodes at 250-300 ℃.
Dry etching: use ICP (inductively coupled plasma etching) to carry out etching.
Technical scheme of the present invention is as follows:
The inhomogeneity method of a kind of raising Sapphire Substrate epitaxial layer of gallium nitride may further comprise the steps:
(1) utilizes laser scribing means that Sapphire Substrate is carried out laser scribing, mark the square-shaped patterns of 0.1mil * 0.1mil~100mil * 100mil with laser at Sapphire Substrate front or the back side, make the sapphire flat substrate.
(2) adopt mocvd method growing GaN epitaxial loayer in gained sapphire flat substrate.For the preparation of LED.
Preferred 10mil * the 10mil of square-shaped patterns size~30mil * 30mil described in the step in the said method (1).
Laser scribing described in the step in the said method (1), the preferred 2 μ m of scratch depth~10 μ m, the preferred 0.5 μ m of width~5 μ m.
Said method is take the positive scribing of the Sapphire Substrate of embodiment 1 as concrete preferred version.
The inhomogeneity method of a kind of raising Sapphire Substrate epitaxial layer of gallium nitride may further comprise the steps:
1) utilizes laser scribing means that Sapphire Substrate is carried out laser scribing, mark the square-shaped patterns of 0.1mil * 0.1mil~100mil * 100mil with laser at Sapphire Substrate front or the back side, make the sapphire flat substrate.
2) in step 1) on the sapphire flat substrate front, SiN or the SiO of evaporation one deck 100nm~500nm
2Mask; Such as Fig. 2.Be coated with one deck photoresist at mask layer, utilize photoresist with the figure of photolithography plate design, transfer on the square-shaped patterns zone mask layer of 0.1mil * 0.1mil~100mil * 100mil, after the development, peel off the mask on the photoresist, keep the mask on the figure, use washed with de-ionized water, the mask pattern of formation rule is such as Fig. 3;
3) with step 2) substrate that makes carries out etching, obtains the sapphire pattern substrate of mask layer; Recycling hydrofluoric acid solution erosion removal mask, flushing, drying obtain the sapphire pattern substrate that laser scribing is crossed; The sapphire pattern substrate of crossing at this laser scribing adopts mocvd method growing GaN epitaxial loayer, for the preparation of LED.
The sapphire pattern substrate of front laser scribing preparation as shown in Figure 4; The sapphire pattern substrate of backside laser scribing preparation, as shown in Figure 5.
Step 1 in the said method) laser scribing described in, scratch depth 2 μ m~10 μ m, width 0.5 μ m~3 μ m.
Step 1 in the said method) the preferred 10mil * 10mil of the size of square-shaped patterns described in~30mil * 30mil.
Step 2 in the said method) mask pattern described in is circular, and diameter is 2 μ m~3 μ m.
Step 3 in the said method) cleaning described in is first each ultrasonic 10min in acetone, ethanol respectively, uses deionized water rinsing again.
Step 2 in the said method) etching described in is by prior art, and wet etching or dry etching all can.
Said method is take embodiment 2,4 as concrete preferred version.
Sapphire flat substrate or graph substrate mocvd method growing GaN epitaxial loayer above-mentioned laser scribing is crossed because laser scribing with the Sapphire Substrate Stress Release, reduces the stress that produces in the growth course, improve the uniformity of GaN epitaxial loayer.
Characteristics of the present invention and excellent results are as follows:
1, the present invention is with the Sapphire Substrate laser scribing, the sapphire flat substrate of gained can be directly used in mocvd method growing GaN epitaxial loayer, because laser scribing can discharge stress first, produces tensile stress in the GaN growth course, substrate is outwards stretched, thereby reduce the substrate warpage degree.
2, the present invention at first marks square-shaped patterns with laser with it with Sapphire Substrate, then prepare for example circular pattern by the sapphire pattern substrate technology, and then the growing GaN epitaxial loayer, because the Sapphire Substrate great majority are concave surfaces, downsagging, after laser scribing streaks, stress is discharged first, and then growing GaN produces tensile stress in the GaN growth course, substrate is outwards stretched, thereby reduce angularity.Thereby solved sapphire growth GaN lattice mismatch, produced stress larger, the problem that epitaxial loayer easily splits and uniformity is relatively poor.
3, the GaN of method Sapphire Substrate of the present invention growth is for the preparation of LED, can be after making tube core direct sliver on former, reduce the step sliver operation in the subsequent technique, save time, laser scribing is crossed the inclined-plane of generation, can increase the tube core bright dipping.
Description of drawings
Fig. 1 is the vertical view of the Sapphire Substrate prepared by laser scribing.Horizontal, vertical straight line is laser scratch among the figure.
Fig. 2 is the schematic diagram of making the PSS figure in laser scribing square-shaped patterns zone.With the signal of the figure in the lattice, be that the PSS figure in the laser scribing zone is seen in the front only.
Fig. 3 makes the graph substrate mask behind the laser scribing of front.Fig. 4 is the graph substrate of producing behind the laser scribing of front.
Fig. 5 makes graph substrate in the front in according to the scribing rear region after the backside laser scribing.The zone that positive etching figure correspondence the backside laser paddle-tumble.
Wherein, 1, Sapphire Substrate, 2, photoresist (mask pattern), 3, SiO
2Film, 4, sapphire pattern substrate (PSS figure).
Embodiment
Below in conjunction with embodiment the present invention is done through a step explanation.The laser scribing means that uses among the embodiment is this area conventional equipment, model: AS2112, and Newwave company produces.The Sapphire Substrate of using among the embodiment is the brilliant U.S. 2 inches substrates in Taiwan.
Embodiment 1:
Improve the inhomogeneity method of sapphire flat substrate epitaxial layer of gallium nitride, step is as follows:
(1) Sapphire Substrate is packed in the laser scribing means; Fixedly Sapphire Substrate is adsorbed on the plant bottom case by vacuum mode on blue film; Sapphire Substrate front or the back side are drawn the square-shaped patterns of upper 10mil * 10mil by laser (1.3W), scratch depth 6 μ m, positive scribing schematic diagram such as Fig. 1;
(2) positive by MOCVD growing GaN epitaxial loayer in the sapphire flat substrate that makes, prepare LED by prior art.
Embodiment 2:
Improve the inhomogeneity method of sapphire pattern substrate epitaxial layer of gallium nitride, step is as follows:
1) Sapphire Substrate is packed in the laser scribing means; Fixedly Sapphire Substrate is adsorbed on the plant bottom case by vacuum mode on blue film; With the positive square-shaped patterns of drawing upper 10mil * 10mil of Sapphire Substrate, see Fig. 1 by laser (1.3W); Scratch depth 5 μ m, width 1 μ m;
2) on the sapphire front, steam the thick SiO of last layer 200nm by the method for evaporation
2Mask; Be coated with the last layer photoresist at mask layer, utilize photoresist with the photoetching circular pattern, diameter 2 μ m, transfer on the square-shaped patterns zone mask layer of 10mil * 10mil, utilize photoetching that version is exposed, 20 seconds time for exposure, develop after 60 seconds, developer solution is alkaline solution; Toasted 30 minutes, corrosion (or etching) mask layer removes photoresist according to a conventional method, and washed with de-ionized water is complete, and the mask pattern of formation rule is seen Fig. 3;
3) with step 2) the existing wet etching technique of the substrate utilization that makes carries out etching, namely in the mixed solution of sulfuric acid and phosphoric acid, carry out etching in 250-300 ℃, after etching is finished, utilize hydrofluoric acid solution to remove mask, by acetone, ethanol, washed with de-ionized water namely obtains required sapphire pattern substrate, sees Fig. 4;
4) the above-mentioned sapphire pattern substrate for preparing is passed through the MOCVD growing GaN, for the preparation of LED.
Embodiment 3:
As described in Example 2, difference is the square-shaped patterns of only drawing 10mil * 10mil at the Sapphire Substrate back side.
Embodiment 4:
Improve the inhomogeneity method of sapphire pattern substrate epitaxial layer of gallium nitride, step is as follows:
1) Sapphire Substrate is packed in the laser scribing means; Fixedly Sapphire Substrate is adsorbed on the plant bottom case by vacuum mode on blue film; The sapphire back side is drawn the square-shaped patterns of upper 20mil * 20mil by laser (1.3W), scratch depth 7 μ m, width 2 μ m;
2) on the sapphire front, steam the thick SiN mask of last layer 300nm by the method for evaporation; Be coated with the last layer photoresist at mask layer, utilize photoresist that diameter 2.5 μ m circular patterns are transferred on the square-shaped patterns zone mask layer of 20mil * 20mil, utilize photoetching that version is exposed, 20 seconds time for exposure, develop after 60 seconds, developer solution is alkaline solution; Toasted 30 minutes, corrosion (or etching) mask layer removes photoresist according to a conventional method, and washed with de-ionized water is complete, the mask pattern of formation rule;
3) with step 2) the existing dry etching technology of the substrate utilization that makes carries out etching, adopts BCl
3And Cl
2Gas etching after etching is finished, utilizes hydrofluoric acid solution to remove mask, and by acetone, ethanol, washed with de-ionized water namely obtains required sapphire pattern substrate, sees Fig. 4;
4) the above-mentioned sapphire pattern substrate for preparing is passed through the MOCVD growing GaN, for the preparation of LED.
The sapphire pattern substrate epitaxial layer of gallium nitride of test implementation example 1-4, method of testing adopt the X-Ray swing curve to test the uniformity of 102 half-peak breadths and photoluminescence spectrum test GaN growth, and test data is listed in the table below:
Sample |
X-Ray (102) half-breadth (s) |
Uniformity |
Embodiment |
1 is just drawing the sapphire flat substrate |
286 |
3.3 |
Embodiment 2 is just drawing sapphire pattern substrate |
251 |
3.1 |
Embodiment 3 back ofs the body are drawn sapphire pattern substrate |
284 |
3.6 |
Embodiment 4 back ofs the body are drawn sapphire pattern substrate |
255 |
3.5 |
Sapphire pattern substrate without laser scribing |
326 |
4.0 |
Illustrate: without the sapphire pattern substrate of laser scribing, the substrate graph preparation method is identical with embodiment 2, does not just carry out laser scribing.
Conclusion: according to above contrast as can be known, method of the present invention has improved epitaxy of gallium nitride layer growth uniformity and GaN-LED quality.