CN101271947A - Controllable asymmetric doping potential barrier nano silicon based luminous device and method for producing the same - Google Patents
Controllable asymmetric doping potential barrier nano silicon based luminous device and method for producing the same Download PDFInfo
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Abstract
The invention relates to an nc-Si based luminescent device based on a controllable asymmetric quantum well structure doping with voltage barrier and a preparation method thereof, which belongs to the technical field of nano-electronics and nano-photoelectronic device material. The luminescent device is deposited with an amorphous carborundum thin film doping with boron as a cavity barrier layer on a semiconductor substrate; the cavity barrier layer is deposited with an nc-Si film which is generated by the anneal of an amorphous silicon film and is used as a luminescent active layer; the luminescent active layer is deposited with an amorphous silicon dioxide thin film doping with phosphor which is used as an electronic barrier layer; the electronic barrier layer is deposited with a conductive film which is left with an optical window and used as the cathode of the luminescent device, while the back side of the semiconductor substrate is deposited with a conductive film which is used as the anode of the luminescent device. The technical process of the invention relates to that a multi-layer film with the quantum well structure is prepared; then annealing and crystallization are processed and the electrodes of the device are prepared. The luminescent device has the advantages of high efficient and balanced current carrier injection structure and the Si/SiO2 luminescent system, which provides the possibility of the realization of a high efficient Si-based luminescent device.
Description
Technical field
The present invention relates to a kind of si-based light-emitting device, especially a kind of nano silicon based luminous device based on controlled asymmetric doping potential barrier quantum well structure also relates to its preparation method simultaneously, belongs to nanoelectronic and nano photoelectronic devices material technology field.
Background technology
Silica-based microelectric technique has become the basis of modern electronic technology, has created the information age of current develop rapidly, and has caused the dramatic change of social life.But along with improving constantly of microelectronic component integrated level, existing device will reach its physics limit, facing to many new challenges such as physical mechanism, time delay, technologies.Under above-mentioned background, people's sight from electrical steering photon, attempt with the carrier of photon as information.Yet at the photoelectricity integration field, crystalline silicon (c-Si) material itself but is not to be well suited for being used for making photoelectric device: its carrier mobility is low, and is indirect gap semiconductor.
At present, the method for improving the silicon characteristic can be divided into two classes: (1) impurity and defect project are about to wait electronics impurity or rare earth ion to be incorporated in the silicon materials, as the complex centre; (2) energy band engineering, by reducing dimension structure silicon materials, the photoelectric characteristic of this silicon materials can artificially " be cut out ".In recent ten years, utilize the silica-based low dimensional structures of energy band engineering preparation to continue to bring out, all belong to this class material as porous silicon, nano-silicon, silicon quantum wire, SiGe strained layer heterojunction and silicon oxide compound low-dimensional system etc.
For silicon oxide compound low-dimensional system, it is represented as the silicon dioxide (SiO of embedding nano silicon (nc-Si) crystal grain
2) or nano-silicon (nc-Si)/silicon dioxide quantum well structure, as the si-based light-emitting device of light-emitting active layer, its advantage is that nano-silicon surface stability and rigidity are more much better than porous silicon, and the photoluminescence efficiency height.This be because the band gap of silicon dioxide big (～9eV), after it constituted heterostructure with silicon, being with to be offset of conduction band and valence band reached 3.15eV and 4.55eV (as shown in Figure 1) respectively, thereby SiO
2/ c-Si/SiO
2The quantum well of forming all has very strong quantum limitation effect to electronics and hole, and the constraint effect of exciton is strong, helps improving luminous efficiency.Secondly, SiO
2Be a kind of desirable passivating film on Si surface, manufacture craft and quality control be unusual mature and reliable all, and be compatible mutually with current microelectronic technique.And, the luminescence generated by light of silicon oxide compound low-dimensional system research in recent years makes substantial progress, it is encouraging L.Pavesi seminar in 2000 from experimentally having verified the gain of light of embedding nano silicon under the short-wave laser pumping the silicon dioxide, and this is the gain of light and the integrated preferred light source of following photoelectricity under the silicon oxide compound low-dimensional system electric pump Pu---the realization of electric pump Pu total silicon base laser has proposed may.
Yet on the whole, the electroluminescent device of silicon oxide compound low-dimensional system progress is slower at present, and subject matter is low, the poor stability of electroluminescent efficiency.This has many-sided reason, and except hanging down because of the radiation recombination efficient that influences charge carrier of quality of forming film, the injection efficiency of nano-silicon density and charge carrier and harmony thereof also have very big influence.Because SiO
2With being with skew to reach 3.15eV and 4.55eV respectively in the monocrystalline silicon formation quantum well, this is higher potential barrier for charge carrier, more seriously conduction band and valence band can be with skew different, make electronics be injected in the nano-silicon than the easier potential barrier of crossing in hole, cause the non-equilibrium injection of electron hole, reduce the radiation recombination efficient of charge carrier of nano-silicon or relative luminescence center and the luminous efficiency of device greatly.The method of the raising injection efficiency that numerous research group both domestic and external proposes can comprise: (1) improves the interface between electrode and the light-emitting active layer, reduces contact resistance, improves the efficient that charge carrier injects light-emitting active layer.(2) select for use calcium low workfunction metal such as (Ca) as device cathodes, select for use gold (Au), nickel high-work-function metals such as (Ni) as anode, reduce the tunneling barrier of electrode and light-emitting active layer, improved injection efficiency ([2] Appl.Phys.Lett.2005,86:193506), (3) in substrate surface structure pyramid structure, make surface roughening, this structure shape such as point electrode, strengthened tunnelling, help charge carrier and inject light-emitting active layer from it, improved the electric current injection efficiency ([3] Appl.Phys.Lett.2006,89:093126).Said method all is to have improved the injection efficiency of charge carrier from the electrode to the light-emitting active layer, still, understands according to the applicant, and the different charge carriers that cause of skew of being with that also do not solve effectively at present because of conduction band and valence band inject the method for imbalance problem.The injection efficiency that how to improve the hole can balance each other it with the injection efficiency of electronics and is still a technical barrier that needs to be resolved hurrily, the luminous efficiency that improves device is had important practical significance.
Summary of the invention
The objective of the invention is to: at the problem of above prior art existence, dual-purpose can be with and the doping engineering, propose a kind of controlled asymmetric doping potential barrier nano silicon based luminous device (for example controlled boron doped amorphous silicon carbide/nano-silicon/phosphorus doping amorphous silica or boron doping amorphous silicon nitride/nano-silicon/phosphorus doping amorphous silica and other similar structures), thereby raising is based on the efficient of charge carrier (electronics and hole) the balance injection of the nano silicon based luminous device of this structure and the efficient of radioluminescence.Provide the preparation method compatible mutually simultaneously, thereby satisfy the demand of development in science and technology for the silicon optoelectronic device with current microelectronic technique.
In order to reach above purpose, recognize after applicant's research, if with SiO
2/ c-Si/SiO
2Trap material in the quantum well changes required low-dimensional luminescent material---nano-silicon into by monocrystalline silicon (c-Si), then the nano-silicon band gap is understood broadening, its restriction can be inversely proportional to the reduction effective mass of electronics (or hole), because the reduction effective mass of electronics is little more a lot of than the hole, so can be with mainly at conduction band part broadening, the tunneling barrier of electronics can significantly reduce and the tunneling barrier in hole changes not quite, and then both difference can further widen.Each sublayer of required quantum well all is no more than ten nanometers, it then no matter is the F-N tunnelling under the High-Field, still low direct Tunneling (or tunnelling mechanism of other form) after the match, tunnelling current generally all reduces with the increase of potential barrier, and electronics directly influences its tunnelling probability with the different tunneling barriers in hole, under the identical condition of other parameter, electronics and hole are seriously uneven to the injection of nano-silicon, compare electronics, the hole is difficult to inject, thereby the radiation recombination probability of electron hole pair is very little in the nano-silicon.Though the electronics in the nano-silicon can produce electron-hole pair by the collision ionization under electric field action radiation recombination takes place, because the participation of phonon is arranged, the luminous efficient of device is difficult to improve, and stability is bad.
If with the barrier layer of hole injection end by SiO
2Change and make Si
3N
4, i.e. SiO
2/ c-Si/Si
3N
4Heterostructure quantum well, and silicon nitride (Si
3N
4) with constitute heterostructure with monocrystalline silicon after, being with to be offset to reach respectively of conduction band and valence band is 2.2eV and 1.8eV, as shown in Figure 2.Si so, so
3N
4The tunneling barrier in the hole of one side is reduced to 2.1eV, and promptly the tunneling barrier of hole end has reduced 2.7eV; The electronics injection end is because cathode material aluminium and tunnel layer SiO
2All do not have no-load voltage ratio, then the tunneling barrier of electronics still remains 3.2eV, and difference of them is 0.9eV, has promptly strengthened the injectability in hole, and has significantly alleviated the unbalanced problem of injecting.If we are with hole barrier layer Si
3N
4Change and make amorphous silicon nitride (a-SiNx), because its band gap can then can be regulated and control the tunneling barrier in hole more neatly with nitrogen silicon than adjustable.
Except that silicon nitride, the semiconductor of other greater band gap (as carborundum SiC) also can be used as hole injection end potential barrier; In like manner, noncrystalline silicon carbide (a-SiCx) substitutes the a-SiCx/nc-Si/SiO that amorphous silicon nitride is formed as hole barrier layer
2Quantum well structure also has and a-SiNx/nc-Si/SiO
2The characteristics of structural similarity.
Based on above-mentioned improved controlled asymmetric barrier quantum well structure, if mix, can change the Fermi level of barrier layer material, thereby change the work function difference of electrode material and barrier layer material by p type or n.With Al/a-SiO
2/ nc-Si/a-SiCx/p-Si substrat structure is an example, can be at amorphous silica (a-SiO
2) in carry out the n type and mix (mixing phosphorus), in noncrystalline silicon carbide, carry out the p type and mix (mixing boron), the result makes on the Fermi level of amorphous silica and moves, the Fermi level of noncrystalline silicon carbide moves down, and as shown in Figure 3, so just forms a p-i-n structure.Move on the Fermi level of amorphous silica the work function difference of itself and aluminium electrode is reduced, thereby further reduce the injection barrier of electronics; The Fermi level of noncrystalline silicon carbide moves down also corresponding the reducing of work function difference that makes itself and p type silicon substrate, thereby has further reduced the injection barrier in hole.Therefore, by the doping content of phosphorus, boron in the control barrier layer, thereby the bias size of scalable Fermi level can change the tunneling barrier in electronics, hole independently; Simultaneously, can also be by the ratio of component (as the nitrogen silicon ratio in the ratio of the carbon silicon in the noncrystalline silicon carbide, the amorphous silicon nitride) that changes the hole barrier layer material, the band gap of regulating hole barrier layer, thereby but the injection barrier of independent regulation hole end.So, as the influence of the different effective masses in thickness that hold concurrently to consider two barrier layers and electronics and hole to tunnelling, under suitable bias voltage, can make the comparatively injection nano-silicon of balance of electronics and hole, so, the electron-hole pair that forms in the nano-silicon carries the baby and the probability that carries out the band edge recombination luminescence becomes big, and the internal quantum efficiency of device increases thereupon.That is, can improve injection efficiency and both injections of balance in electronics, hole by making up controlled asymmetric doping potential barrier quantum well structure, thereby improve efficient based on the nano silicon based luminous device of this structure.
Therefore, controlled asymmetric doping potential barrier quantum well structure (B-dopeda-SiCx/nc-Si/P-doped a-SiO for example
2) or B-doped a-SiNx/nc-Si/P-dopeda-SiO
2And other similar structures) with intrinsic SiO
2/ nc-Si/SiO
2Compare, can reduce the tunneling barrier of electronics and hole end, effectively improve charge carrier simultaneously and inject unbalanced chronic illness, improve the internal quantum efficiency of luminescent device; Simultaneously, compare with structures such as a-SiNx/nc-Si/a-SiNx or a-SiCx/nc-Si/a-SiCx, new construction has kept Si/SiO again
2System gets a good chance of realizing the gain of light the electric pump Pu under because this system has realized the gain of light under the short-wave laser pumping, the multilevel system of its existence, also provides possible for the realization of nano-silicon laser simultaneously.
On this understanding basis, one of solution of the present invention is: controlled asymmetric doping potential barrier nano silicon based luminous device, comprise p N-type semiconductor N substrate, on described p N-type semiconductor N substrate, be deposited with boron doped amorphous silicon carbide film (B-doped a-SiCx) as hole barrier layer; The Nano thin film that is deposited with amorphous silicon membrane (a-Si) annealing back generation on described hole barrier layer is as light-emitting active layer; On described light-emitting active layer, be deposited with amorphous silica film (the P-doped a-SiO of phosphorus doping
2) as electron barrier layer; Deposit leaves the conductive film of optical window as the luminescent device negative electrode on described electron barrier layer; The back side of described p N-type semiconductor N substrate is deposited with conductive film as anode.
Two of solution of the present invention is: controlled asymmetric doping potential barrier nano silicon based luminous device, comprise n N-type semiconductor N substrate, and on described n N-type semiconductor N substrate, be deposited with amorphous silica film (the P-doped a-SiO of phosphorus doping
2) as electron barrier layer; The Nano thin film that is deposited with amorphous silicon membrane (a-Si) annealing back generation on described electron barrier layer is as light-emitting active layer; On described light-emitting active layer, be deposited with boron doped amorphous silicon carbide film (B-doped a-SiCx) as hole barrier layer; The conductive film that deposit leaves optical window on described hole barrier layer is as the luminescent device anode, and the back side of described n N-type semiconductor N substrate is deposited with conductive film as negative electrode.
The controlled asymmetric doping potential barrier nano silicon based luminous device of one of technique scheme of the present invention (based on controlled boron doped amorphous silicon carbide/nano-silicon/phosphorus doping amorphous silica---B-doped a-SiCx/nc-Si/P-doped a-SiO
2The nano silicon based luminous device of quantum well structure) preparation process may further comprise the steps:
First step, preparation have the plural layers (as: utilizing plasma enhanced chemical vapor deposition (PECVD) technology) of quantum well structure
1-1, employing silane (SiH
4), methane (CH
4) and borine (B
2H
6) mist as reactant gas source, deposit obtains (usually thickness be no more than 10nm) boron doping hydrogenated amorphous silicon carbide (B-doped a-SiCx:H) film on p N-type semiconductor N substrate;
1-2, employing silane (SiH
4) as reactant gas source, on described boron doped hydrogenated amorphous silicon carbide film (B-doped a-SiCx:H), make silane decompose deposit and generate (thickness is no more than 5nm usually) amorphous silicon hydride (a-Si:H) film;
1-3, employing silane (SiH
4) and phosphine (PH
3) as reactant gas source, go up deposit (thickness is no more than 5nm usually) at hydrogenation non crystal silicon film (a-Si:H) and mix the phosphorus hydrogenation non crystal silicon film;
1-4, employing oxygen (O
2) as source of the gas, will mix hydrogenated amorphous silicon dioxide (the P-doped a-SiO that phosphorus hydrogenation non crystal silicon film plasma in-situ oxidation generates (thickness is no more than 10nm usually) phosphorus doping
2: H) film;
Second step, reprocessing annealing crystallization (with reference to conventional semiconductor heat treatment process)
2-1, the p N-type semiconductor N substrate sample that has the quantum well structure plural layers that previous step is obtained are suddenly carried out the preliminary treatment of constant temperature dehydrogenation annealing, the a large amount of hydrogen that make in the plural layers to be contained are steadily deviate from film, prevent that plural layers from breaking in follow-up high annealing; Make boron doped hydrogenated silicon carbide (B-doped a-SiCx:H) film become boron doped noncrystalline silicon carbide (B-doped a-SiCx) film; Make amorphous silicon hydride (a-Si:H) film dehydrogenation becoming amorphous silicon (a-Si) film; Make the hydrogenated amorphous silica membrane (P-dopeda-SiO of phosphorus doping
2: H) become amorphous silica (the P-doped a-SiO of phosphorus doping
2) film;
2-2, the pretreated sample of constant temperature dehydrogenation annealing is carried out quick thermal annealing process, make amorphous silicon (a-Si) film nucleation, crystallization;
2-3, the sample cycle annealing after the quick thermal annealing process is handled, make the nuclei of crystallization that generate in amorphous silicon (a-Si) film continue to grow up, generate amorphous silica film (the P-doped a-SiO that is clipped in boron doped amorphous silicon carbide film (B-doped a-SiCx) and phosphorus doping
2) between nano silicon quantum dots, with as light-emitting active layer;
The electrode of third step, fabricate devices
3-1, at amorphous silica (P-dopeda-SiO as the phosphorus doping of electron barrier layer
2) on the film deposit leave the conductive film of optical window as the luminescent device negative electrode;
3-2, at the anode of p N-type semiconductor N substrate back deposit conductive film as luminescent device.
Two controlled asymmetric doping potential barrier nano silicon based luminous device of technique scheme of the present invention (based on controlled boron doped amorphous silicon carbide/nano-silicon/phosphorus doping amorphous silica---B-doped a-SiCx/nc-Si/P-doped a-SiO
2The nano silicon based luminous device of quantum well structure) preparation process may further comprise the steps:
First step, preparation have the plural layers of quantum well structure
1-1, employing silane (SiH
4) and phosphine (PH
3) mist as reactant gas source, deposit obtains phosphorus doping amorphous silicon hydride (P-doped a-Si:H) film of (usually thickness be no more than 5nm) on n N-type semiconductor N substrate;
1-2, employing oxygen (O
2) as source of the gas, will mix hydrogenated amorphous silicon dioxide (the P-doped a-SiO that phosphorus hydrogenation non crystal silicon film plasma in-situ oxidation generates (thickness is no more than 10nm usually) phosphorus doping
2: H) film;
1-3, employing silane (SiH
4) as reactant gas source, on the hydrogenated amorphous silica membrane of described phosphorus doping, make silane decompose deposit and generate (thickness is no more than 5nm usually) amorphous silicon hydride (a-Si:H) film;
1-4, employing silane (SiH
4), methane (CH
4) and borine (B
2H
6) mist as reactant gas source, deposit obtains boron doping hydrogenated amorphous silicon carbide (B-doped a-SiCx:H) film of (usually thickness be no more than 10nm) on hydrogenation non crystal silicon film;
Second step, reprocessing annealing crystallization (with reference to conventional semiconductor heat treatment process)
2-1, the n N-type semiconductor N substrate sample that has the quantum well structure plural layers that previous step is obtained are suddenly carried out the preliminary treatment of constant temperature dehydrogenation annealing, the a large amount of hydrogen that make in the plural layers to be contained are steadily deviate from film, prevent that plural layers from breaking in follow-up high annealing; Make boron doped hydrogenated silicon carbide (B-doped a-SiCx:H) film become boron doped noncrystalline silicon carbide (B-doped a-SiCx) film, make amorphous silicon hydride (a-Si:H) film dehydrogenation becoming amorphous silicon (a-Si) film; Make the hydrogenated amorphous silica membrane (P-dopeda-SiO of phosphorus doping
2: H) become amorphous silica (the P-doped a-SiO of phosphorus doping
2) film;
2-2, the pretreated sample of constant temperature dehydrogenation annealing is carried out quick thermal annealing process, make amorphous silicon (a-Si) film nucleation, crystallization;
2-3, the sample cycle annealing after the quick thermal annealing process is handled, make the nuclei of crystallization that generate in amorphous silicon (a-Si) film continue to grow up, generate amorphous silica film (the P-doped a-SiO that is clipped in boron doped amorphous silicon carbide film (B-doped a-SiCx) and phosphorus doping
2) between nano silicon quantum dots, with as light-emitting active layer;
The electrode of third step, fabricate devices
3-1, deposit leaves the conductive film of optical window as the luminescent device anode on as boron doped noncrystalline silicon carbide (B-dopeda-SiCx) film of hole barrier layer;
3-2, at the negative electrode of n N-type semiconductor N substrate back deposit conductive film as luminescent device.
All noncrystalline silicon carbides in two kinds of schemes of above technology all can replace with amorphous silicon nitride, only need the methane gas in the preparation process is got final product with the ammonia replacement, therefore hereinafter represent noncrystalline silicon carbide or amorphous silicon nitride, show methane or ammonia with the methane/ammonia gas meter with amorphous carbon/silicon nitride.
Through above step, can finish the preparation of controlled asymmetric doping potential barrier nano silicon based luminous device.Advantage of the present invention can be summarized as follows:
1, adopts the controlled a-SiCx (or a-SiNx) of band gap as hole barrier layer, can reduce original SiO
2/ nc-Si/SiO
2Gap in the quantum well structure between the tunneling barrier in electronics and hole improves the injection efficiency in hole, significantly improves charge carrier and injects unbalanced problem.
2, n type doping (mixing phosphorus) is carried out in employing in amorphous silica, in noncrystalline silicon carbide, carry out p type doping (mixing boron), make on the amorphous silica Fermi level move, the Fermi level of noncrystalline silicon carbide moves down, form a p-i-n structure, make between the electronics injection end material respectively, the work function difference between the injection end material of hole all reduces, thereby further reduced the injection barrier of charge carrier; By the doping content of phosphorus, boron in the control barrier layer, thereby the side-play amount of scalable Fermi level can change the tunneling barrier in electronics, hole independently, makes charge carrier inject more evenly.
3, owing to the existence of asymmetric barrier, electronics that more injections are entered and hole can be limited in the nano-silicon zone and radiation recombination can take place, and have increased electronics and the luminous internal quantum efficiency of hole-recombination in the luminescent device.Simultaneously, new construction has kept Si/SiO
2System is expected to realize the gain of light and the laser under the electric pump Pu equally because this system has realized the gain of light under the short-wave laser pumping, the multilevel system of its existence.So new construction had both been considered the raising of charge carrier injection efficiency, the improvement of injecting balance and the raising of device internal quantum efficiency, had taken into account Si/SiO again
2The advantage of system aspect the realization gain of light and electric pump laser.
4, adopted relative high dielectric constant material such as noncrystalline silicon carbide (a-SiCx), amorphous silicon nitride (a-SiNx) to replace amorphous silica as hole injection end barrier layer, can suitably increase film thickness, avoid the problem of all using the caused leakage current of ultra-thin silicon dioxide to increase.
5, low temperature preparation, technology is simple, and is compatible mutually with modern microelectronics silicon technology.
So B-doped a-SiCx/nc-Si/P-doped a-SiO of the present invention
2(or B-doped a-SiNx/nc-Si/P-doped a-SiO
2) controlled asymmetric doping potential barrier nano silicon based luminous device has concurrently efficiently, the charge carrier injecting structure and the Si/SiO of balance
2The advantage of luminescence system two aspects, for the realization of efficient si-based light-emitting device even total silicon base laser provides may.
Description of drawings
Fig. 1 is Al/a-SiO
2/ c-Si/a-SiO
2When being zero ,/p-type Si structure bias voltage can be with schematic diagram.
Fig. 2 is Al/a-SiO
2/ c-Si/Si
3N
4When being zero ,/p-type Si structure bias voltage can be with schematic diagram.
Fig. 3 is based on controlled B-doped a-SiCx/nc-Si/P-doped a-SiO
2When being zero, the nano silicon based luminous device bias voltage of asymmetric doping potential barrier quantum well structure can be with schematic diagram, the original intrinsic a-SiO of expression of black broken string among the figure
2With Fermi level position in the energy band diagram after doping of intrinsic a-SiCx, to make comparisons.
Fig. 4 be with on the p type silicon substrate based on controlled B-doped a-SiCx/nc-Si/P-dopeda-SiO
2The nano silicon based luminous device cross-section structure of asymmetric doping potential barrier quantum well structure and the circuit diagram of testing its room temperature electroluminescent, illustration are to overlook photo as the front of the aluminum annular-shaped electrode of negative electrode.
Embodiment
Embodiment one
The controlled asymmetric doping potential barrier nano silicon based luminous device of present embodiment is selected Al/P-doped a-SiO for use
2/ nc-Si/B-doped a-SiCx/p-type Si device architecture, the preparation implementation process is as follows:
First step, utilize plasma enhanced chemical vapor deposition (PECVD) technology, preparation has the plural layers of quantum well structure
1-1, preparation boron doping hydrogenated amorphous silicon carbide (B-doped a-SiCx:H) film are as barrier layer: utilize capacity plate antenna type radio frequency plasma to strengthen chemical vapour deposition (CVD) (PECVD) system, substrate is placed on the metallic anode plate of ground connection in the reaction chamber, adopts silane (SiH
4), methane (CH
4) and borine (B
2H
6) mist of (borine is by diluted in hydrogen, and concentration is 1%) is as reactant gas source, deposit obtains being no more than the thick boron doped a-SiCx:H film of 10nm (for example 0.2-10nm).During deposit, gas flow ratio is preferably SiH
4: CH
4: B
2H
6=1: 10: 5.Some other process conditions of during preparation are as follows:
Power source frequency: 13.56MHz,
Power density: 0.32-0.53W/cm
2,
Underlayer temperature: 250 ℃.
1-2, preparation amorphous silicon hydride (a-Si:H) film are as potential well layer: utilize capacity plate antenna type radio frequency plasma to strengthen chemical vapour deposition (CVD) (PECVD) system, adopt silane (SiH
4) as reactant gas source, on described boron doped hydrogenated amorphous silicon carbide film (B-dopeda-SiCx:H), make silane under aura, decompose deposit and generate amorphous silicon hydride (a-Si:H) film.During deposit, silane flow rate is 5sccm, and deposition time is 6s-20s, and reaction chamber pressure is 30mtor, the thickness of the hydrogenation non crystal silicon film that obtains is no more than 5nm (for example 0.1-5nm), identical among the power source frequency of system during preparation, power density, underlayer temperature and the step 1-1.Phosphorus amorphous silicon hydride (P-doped a-Si:H) film is mixed in 1-3, preparation: utilize capacity plate antenna type radio frequency plasma to strengthen chemical vapour deposition (CVD) (PECVD) system, adopt silane (SiH
4) and phosphine (PH
3) mist of (phosphine is by diluted in hydrogen, and concentration is 1%) is as reactant gas source, on amorphous silicon hydride (a-Si:H) film, continue deposit be no more than 5nm (for example 0.1-5nm) thick mix the phosphorus hydrogenation non crystal silicon film.During deposit, gas flow ratio is SiH
4: PH
3=1: 10, identical among the power source frequency of system during preparation, power density, underlayer temperature and the step 1-1.
Hydrogenated amorphous silicon dioxide (the P-doped a-SiO of 1-4, preparation phosphorus doping
2: H) film is as barrier layer: utilize capacity plate antenna type radio frequency plasma plasma enhanced chemical vapor deposition (PECVD) system, amorphous silicon hydride (P-doped a-Si:H) the film plasma plasma in-situ oxidation growth of phosphorus doping is no more than the thick phosphorus doping a-SiO of 10nm (for example 0.2-10nm)
2: the H layer.Adopt oxygen (O
2) as reactant gas source, the flow of oxygen is 20sccm, reaction chamber pressure is 130mtorr, oxidization time is 3-10mins, the thickness of the hydrogenation doping amorphous silica layer that obtains is about 0.2-10nm, identical among the power source frequency of system during preparation, power density, underlayer temperature and the step 1-1.
Second step, reprocessing annealing crystallization (with reference to conventional semiconductor heat treatment process)
2-1, constant temperature dehydrogenation annealing preliminary treatment: the p type silicon substrate sample of the band quantum well structure that previous step is obtained, put into high temperature resistance furnace, carry out the constant temperature dehydrogenation annealing preliminary treatment 1 hour of (for example 440-460 ℃) nitrogen atmosphere about 450 ℃, purpose is that a large amount of hydrogen contained in the plural layers are steadily deviate from, make boron doped hydrogenated silicon carbide (B-doped a-SiCx:H) film become boron doped noncrystalline silicon carbide (B-doped a-SiCx) film, make amorphous silicon hydride (a-Si:H) film dehydrogenation becoming amorphous silicon (a-Si) film, make hydrogenated amorphous silica membrane (the P-doped a-SiO of phosphorus doping
2: H) become amorphous silica (the P-doped a-SiO of phosphorus doping
2) film, break in follow-up high annealing to prevent plural layers.2-2, quick thermal annealing process: the pretreated sample of previous step constant temperature dehydrogenation annealing is put into RTP-300 type rapid thermal anneler, carry out the quick thermal annealing process of 1100 ℃ of nitrogen atmospheres, make a-Si nucleation and growth, realize preliminary crystallization.Annealing process is divided four ones: one, rise to 200 ℃ fast to samples pre-heated from room temperature, and the heating-up time is 10s; Two, rise to 1100 ℃ rapidly from 200 ℃, the heating-up time is 10s; Three, carry out 1100 ℃ of constant temperature rapid thermal annealing 50s; Four, natural cooling 15-20mi is below ns to 50 ℃ under the nitrogen atmosphere protection.
2-3, cycle annealing are handled: the sample after the previous step rapid thermal treatment is reentered into high temperature resistance furnace, carries out the cycle annealing of 1100 ℃ of nitrogen atmospheres and handle, the nuclear that previous step is generated continues to grow up, and generates to be clipped in B-doped a-SiCx and P-doped a-SiO
2Nano silicon quantum dots between the layer, the two-dimentional quantum dot array light-emitting active layer in the quantum well structure forms.Annealing process is: one, sample is put into the annealing boiler tube of nitrogen atmosphere, and slowly heating, temperature rises to 1100 ℃ by room temperature through 30mins; Two, cycle annealing is 1 hour in 1100 ℃ of nitrogen atmospheres; Three, stop heating, the nitrogen atmosphere protection is slowly reduced to below 100 ℃ through 40mins down; Four, naturally cool to room temperature.
The metal electrode of third step, fabricate devices
3-1, fabricate devices negative electrode: utilize the electron beam evaporation plating technology, the aluminium film that deposit one deck annular shape on the one side of plural layers is arranged at the sample after the annealing is as device cathodes and light-emitting window.During deposit, sample is tipped upside down on the electrode template that has the annular hole, make sample have the one side of multilayer film to contact with template.Electron beam heating aluminium target, make aluminium steam from lower to upper evaporation to multilayer film.The inner and outer diameter of aluminium ring is respectively 0.1mm and 0.5mm, and film thickness is 200nm, and other main technologic parameters is as follows:
The base vacuum degree is 5.0 * 10
-4Pa, heater current are 300mA, and accelerating voltage is 8kV, and the evaporation time is 5mins, and base reservoir temperature is 150 ℃.
3-2, fabricate devices anode: in the thicker gold thin film of p type silicon substrate back side deposit one deck as the anode contact electrode.During deposit, use the accurate etching plated film instrument of Gatan company, thickness of electrode is 150nm, and other main technologic parameters is as follows: rifle electric current: 350mA, and accelerating voltage: 4Kv, plated film time: 15mins, base vacuum are 10
-4The Pa magnitude.
Embodiment two
Controlled asymmetric doping potential barrier nano silicon based luminous device of present embodiment and preparation method thereof is selected ITO (indium tin oxide)/B-doped a-SiCx/nc-Si/P-dopeda-SiO for use
2/ n-type Si device architecture, implementation process is as follows:
First step, utilize plasma enhanced chemical vapor deposition (PECVD) technology, preparation has the quantum well structure plural layers
Phosphorus amorphous silicon hydride (P-doped a-Si:H) film is mixed in 1-1, preparation: utilize capacity plate antenna type radio frequency plasma to strengthen chemical vapour deposition (CVD) (PECVD) system, n type substrate is placed on the metallic anode plate of ground connection in the reaction chamber, adopts silane (SiH
4) and phosphine (PH
3) mist of (phosphine is by diluted in hydrogen, and concentration is 1%) is as reactant gas source, on amorphous silicon hydride (a-Si:H) film, continue deposit 0.1-5nm thick mix the phosphorus hydrogenation non crystal silicon film.During deposit, gas flow ratio is SiH
4: PH
3=1: 10, some other process conditions of during preparation are as follows:
Power source frequency: 13.56MHz,
Power density: 0.32-0.53W/cm
2,
Underlayer temperature: 250 ℃.
Hydrogenated amorphous silicon dioxide (the P-doped a-SiO of 1-2, preparation phosphorus doping
2: H) film is as barrier layer: utilize capacity plate antenna type radio frequency plasma plasma enhanced chemical vapor deposition (PECVD) system, with the thick phosphorus doping a-SiO of amorphous silicon hydride (P-doped a-Si:H) film plasma in-situ oxidation growth 0.2-10nm of phosphorus doping
2: the H layer.Adopt oxygen (O
2) as reactant gas source, the flow of oxygen is 20sccm, reaction chamber pressure is 130mtorr, oxidization time is 3-10mins, identical during preparation among parameters such as the power source frequency of system, power density, underlayer temperature and the step 1-1
1-3, preparation amorphous silicon hydride (a-Si:H) film are as potential well layer: utilize capacity plate antenna type radio frequency plasma to strengthen chemical vapour deposition (CVD) (PECVD) system, adopt silane (SiH
4) as reactant gas source, at the hydrogenated amorphous silica membrane (P-dopeda-SiO of described phosphorus doping
2: H), make silane under aura, decompose deposit and generate amorphous silicon hydride (a-Si:H) film.During deposit, silane flow rate is 5sccm, and deposition time is 6s-20s, and reaction chamber pressure is 30mtor, the thickness of the hydrogenation non crystal silicon film that obtains is 0.1-5nm, identical during preparation among parameters such as the power source frequency of system, power density, underlayer temperature and the step 1-1.1-4, preparation boron doping hydrogenated amorphous silicon carbide (B-doped a-SiCx:H) film are as barrier layer: utilize capacity plate antenna type radio frequency plasma to strengthen chemical vapour deposition (CVD) (PECVD) system, adopt silane (SiH
4), methane (CH
4) and borine (B
2H
6) mist of (borine is by diluted in hydrogen, and concentration is 1%) is as reactant gas source, the thick boron doped a-SiCx:H film of deposit 0.2-10nm on the amorphous silicon hydride that previous step obtains.During deposit, gas flow ratio is SiH
4: CH
4: B
2H
6=1: 10: 5.Identical among the power source frequency of system during preparation, power density, underlayer temperature and the step 1-1.
Second step, reprocessing annealing crystallization (temperature of following annealing in process, time control can be carried out with reference to the common process of existing semiconductor applications)
2-1, constant temperature dehydrogenation annealing preliminary treatment: the n type silicon substrate sample of the band quantum well structure that previous step is obtained, put into high temperature resistance furnace, carry out the constant temperature dehydrogenation annealing preliminary treatment 1 hour of 450 ℃ of left and right sides nitrogen atmospheres, purpose is that a large amount of hydrogen contained in the plural layers are steadily deviate from, make boron doped hydrogenated silicon carbide (B-doped a-SiCx:H) film become boron doped noncrystalline silicon carbide (B-doped a-SiCx) film, make amorphous silicon hydride (a-Si:H) film dehydrogenation becoming amorphous silicon (a-Si) film, make the hydrogenated amorphous silica membrane (P-dopeda-SiO of phosphorus doping
2: H) become amorphous silica (the P-doped a-SiO of phosphorus doping
2) film, break in follow-up high annealing to prevent plural layers.
2-2, quick thermal annealing process: the pretreated sample of previous step constant temperature dehydrogenation annealing is put into RTP-300 type rapid thermal anneler, carry out the quick thermal annealing process of 1100 ℃ of nitrogen atmospheres, make a-Si nucleation and growth, realize preliminary crystallization.Annealing process is divided four ones: one, rise to 200 ℃ fast to samples pre-heated from room temperature, and the heating-up time is 10s; Two, rise to 1100 ℃ rapidly from 200 ℃, the heating-up time is 10s; Three, carry out 1100 ℃ of constant temperature rapid thermal annealing 50s; Four, natural cooling is below 15-20mins to 50 ℃ under the nitrogen atmosphere protection.
2-3, cycle annealing are handled: the sample after the previous step rapid thermal treatment is reentered into high temperature resistance furnace, carries out the cycle annealing of 1100 ℃ of nitrogen atmospheres and handle, the nuclear that previous step is generated continues to grow up, and generates to be clipped in B-doped a-SiCx and P-doped a-SiO
2Nano silicon quantum dots between the layer, the two-dimentional quantum dot array light-emitting active layer in the quantum well structure forms.Annealing process is: one, sample is put into the annealing boiler tube of nitrogen atmosphere, and slowly heating, temperature rises to 1100 ℃ by room temperature through 30mins; Two, cycle annealing is 1 hour in 1100 ℃ of nitrogen atmospheres; Three, stop heating, the nitrogen atmosphere protection is slowly reduced to below 100 ℃ through 30mins down; Four, naturally cool to room temperature.
The electrode of third step, fabricate devices
3-1, fabricate devices anode: utilize the electron beam evaporation plating technology, indium tin oxide (ITO) transparent conductive film of deposit one deck circle spot shape is as the anode and the light-emitting window of device on the sample after the annealing.During deposit, sample is tipped upside down on the round-meshed electrode template, make sample have the one side of multilayer film to contact with template.Electron beam heating aluminium target, make ITO steam from lower to upper evaporation to multilayer film.The diameter of circle spot shape electrode can be 0.1mm-3mm, and film thickness is 300nm, and the evaporation time is 10mins, and other main technologic parameters is as follows: the base vacuum degree is 5.0 * 10
-4Pa, heater current are 30mA, and accelerating voltage is 8kV, and base reservoir temperature is a room temperature.3-2, fabricate devices negative electrode: at the thicker aluminium film of n type silicon substrate back side deposit one deck as the negative electrode contact electrode.During deposit, utilize the electron beam evaporation plating technology equally, target is changed to aluminium, and thickness of electrode is 1000nm, and the evaporation time is 30mins, the same 3-1 of other main technologic parameters.
Except that above-mentioned example, the present invention can also have other execution mode.All employings are equal to replaces or technical scheme that equivalent transformation forms, and the sub-technical scheme that contains of the art of this patent (superlattice structure of the same material that barrier layer is a component, band gap is adjustable such as [a-SiCx/nc-Si/a-SiCy] n, [a-SiNx/nc-Si/a-SiNy] n for example; A-SiCx/nc-Si/SiO
2, a-SiNx/nc-Si/SiO
2Deng reservation Si/SiO
2The quantum limit structure of system; [SiO
2/ nc-Si/P-doped SiO
2] n, [a-SiCx/nc-Si/P-doped SiO
2] n, [a-SiNx/nc-Si/P-doped SiO
2] n etc. reduces double-barrier single-well or the multi-layer film structure that barrier layer and nano-silicon constitute the side-play amount difference of conduction band and valence band behind the heterojunction by phosphorus doping; The quantum well structure of the tunneling barrier height that [n-type a-SiCx/nc-Si/p-type a-SiCy] n, [n-typea-SiNx/nc-Si/p-type a-SiNy] n etc. change charge carrier by mixing; For another example; Semiconductor substrate such as p+, p-with the various doping contents of similar type replace the p N-type semiconductor N; Semiconductor substrate such as n+, n-with the various doping contents of similar type replace the p N-type semiconductor N) and execution mode, all drop on the protection range of requirement of the present invention.
Claims (8)
1. a controlled asymmetric doping potential barrier nano silicon based luminous device comprises p N-type semiconductor N substrate, it is characterized in that: be deposited with boron doped amorphous carbon/silicon nitride film as hole barrier layer on described p N-type semiconductor N substrate; The Nano thin film that is deposited with amorphous silicon membrane annealing back generation on described hole barrier layer is as light-emitting active layer; The amorphous silica film that is deposited with phosphorus doping on described light-emitting active layer is as electron barrier layer; Deposit leaves the conductive film of optical window as the luminescent device negative electrode on described electron barrier layer; The back side of described p N-type semiconductor N substrate is deposited with conductive film as the luminescent device anode.
2. according to the described controlled asymmetric doping potential barrier nano silicon based luminous device of claim 1, it is characterized in that: described conductive film is a metallic film.
3. according to the described controlled asymmetric doping potential barrier nano silicon based luminous device of claim 2, it is characterized in that: described negative electrode is made of the aluminium film, and described anode is made of gold thin film.
4. controlled asymmetric doping potential barrier nano silicon based luminous device preparation method may further comprise the steps:
First step, preparation have the plural layers of quantum well structure
The mist of 1-1, employing silane, methane/ammonia gas and borine is as reactant gas source, and deposit obtains boron doping hydrogenated amorphous carbon/silicon nitride film on p N-type semiconductor N substrate;
1-2, employing silane, make silane decompose deposit and generate hydrogenation non crystal silicon film on described boron doped hydrogenated amorphous carbon/silicon nitride film as reactant gas source;
1-3, employing silane and phosphine are as reactant gas source, and the phosphorus hydrogenation non crystal silicon film is mixed in deposit on hydrogenation non crystal silicon film;
1-4, employing oxygen will be mixed the hydrogenated amorphous silica membrane that phosphorus hydrogenation non crystal silicon film plasma in-situ oxidation generates phosphorus doping as source of the gas;
Second step, reprocessing annealing crystallization
2-1, the p N-type semiconductor N substrate sample that has the quantum well structure plural layers that previous step is obtained are suddenly carried out the preliminary treatment of constant temperature dehydrogenation annealing, and a large amount of hydrogen that make in the plural layers to be contained are steadily deviate from film; Make boron doped hydrogenated amorphous carbon/silicon nitride film become boron doped amorphous carbon/silicon nitride film; Make the hydrogenation non crystal silicon film dehydrogenation become amorphous silicon membrane; Make the hydrogenated amorphous silica membrane of phosphorus doping become the amorphous silica film of phosphorus doping;
2-2, the pretreated sample of constant temperature dehydrogenation annealing is carried out quick thermal annealing process, make amorphous silicon membrane nucleation, crystallization;
2-3, the sample cycle annealing after the quick thermal annealing process is handled, make the nuclei of crystallization that generate in the amorphous silicon membrane continue to grow up, generation is clipped in the nano silicon quantum dots between the amorphous silica film of boron doped amorphous carbon/silicon nitride film and phosphorus doping, with as light-emitting active layer;
The electrode of third step, fabricate devices
3-1, deposit leaves the conductive film of optical window as the luminescent device negative electrode on as the amorphous silica film of the phosphorus doping of electron barrier layer;
3-2, at the anode of p N-type semiconductor N substrate back deposit conductive film as luminescent device.
5. according to the described controlled asymmetric doping potential barrier nano silicon based luminous device preparation method of claim 4, it is characterized in that: described boron doping hydrogenated amorphous carbon/silicon nitride film thickness is 0.2-10nm; Described hydrogenation non crystal silicon film thickness is 0.1-5nm; The described phosphorus hydrogenation non crystal silicon film thickness of mixing is 0.1-5nm; The hydrogenated amorphous silica membrane thickness of described phosphorus doping is 0.2-10nm.
6. a controlled asymmetric doping potential barrier nano silicon based luminous device comprises n N-type semiconductor N substrate, is deposited with the amorphous silica film of phosphorus doping as electron barrier layer on described n N-type semiconductor N substrate; The Nano thin film that is deposited with amorphous silicon membrane annealing back generation on described electron barrier layer is as light-emitting active layer; On described light-emitting active layer, be deposited with boron doped amorphous carbon/silicon nitride film as hole barrier layer; The conductive film that deposit leaves optical window on described hole barrier layer is as the luminescent device anode, and the back side of described n N-type semiconductor N substrate is deposited with conductive film as negative electrode.
7. controlled asymmetric doping potential barrier nano silicon based luminous device preparation method may further comprise the steps:
First step, preparation have the quantum well structure plural layers
1-1, adopt silane and phosphine mist as reactant gas source, the phosphorus doping hydrogenation non crystal silicon film that deposit obtains on n N-type semiconductor N substrate;
1-2, employing oxygen will be mixed the hydrogenated amorphous silica membrane that phosphorus hydrogenation non crystal silicon film plasma in-situ oxidation generates phosphorus doping as source of the gas;
1-3, employing silane, make silane decompose deposit and generate hydrogenation non crystal silicon film on the hydrogenated amorphous silica membrane of described phosphorus doping as reactant gas source;
1-4, adopt silane, methane/ammonia gas and borine mist as reactant gas source, boron doping hydrogenated amorphous carbon/silicon nitride film that deposit obtains on hydrogenation non crystal silicon film;
Second step, reprocessing annealing crystallization
2-1, the n N-type semiconductor N substrate sample that has the quantum well structure plural layers that previous step is obtained are suddenly carried out the preliminary treatment of constant temperature dehydrogenation annealing, and a large amount of hydrogen that make in the plural layers to be contained are steadily deviate from film; Make boron doped hydrogenated amorphous carbon/silicon nitride film become boron doped amorphous carbon/silicon nitride film, make the hydrogenation non crystal silicon film dehydrogenation become amorphous silicon membrane; Make the hydrogenated amorphous silica membrane of phosphorus doping become the amorphous silica film of phosphorus doping;
2-2, the pretreated sample of constant temperature dehydrogenation annealing is carried out quick thermal annealing process, make amorphous silicon (a-Si) film nucleation, crystallization;
2-3, the sample cycle annealing after the quick thermal annealing process is handled, make the nuclei of crystallization that generate in the amorphous silicon membrane continue to grow up, generation is clipped in the nano silicon quantum dots between the amorphous silica film of boron doped amorphous carbon/silicon nitride film and phosphorus doping, with as light-emitting active layer;
The electrode of third step, fabricate devices
3-1, deposit leaves the conductive film of optical window as the luminescent device anode on as the boron doped amorphous carbon/silicon nitride film of hole barrier layer;
3-2, at the negative electrode of n N-type semiconductor N substrate back deposit conductive film as luminescent device.
8. according to the described controlled asymmetric doping potential barrier nano silicon based luminous device preparation method of claim 7, it is characterized in that: described boron doping hydrogenated amorphous carbon/silicon nitride film thickness is 0.2-10nm; Described hydrogenation non crystal silicon film thickness is 0.1-5nm; The described phosphorus hydrogenation non crystal silicon film thickness of mixing is 0.1-5nm; The hydrogenated amorphous silica membrane thickness of described phosphorus doping is 0.2-10nm.
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2008
- 2008-05-06 CN CNB2008100254996A patent/CN100555693C/en not_active Expired - Fee Related
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| CN106783544A (en) * | 2016-12-23 | 2017-05-31 | 武汉华星光电技术有限公司 | The manufacture method of polysilicon layer and the manufacture method of thin film transistor (TFT) |
| CN108417481A (en) * | 2018-03-22 | 2018-08-17 | 京东方科技集团股份有限公司 | Processing method, thin film transistor (TFT) and the display device of silicon nitride dielectric layer |
| CN108417481B (en) * | 2018-03-22 | 2021-02-23 | 京东方科技集团股份有限公司 | Processing method of silicon nitride dielectric layer, thin film transistor and display device |
| CN110165017A (en) * | 2019-04-18 | 2019-08-23 | 中国科学院宁波材料技术与工程研究所 | Prepare the quick annealing method of tunnelling oxygen passivation contact structures |
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