JP2007063378A - Nano-silicon-containing white light-emitting silicon oxide film and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a nanosilicon-containing silicon oxide film that emits white in a state in which nanosilicon emitting red, green, and blue is contained in a silicon film, obtains white light emission clearly and stably, and emits white light. Establish a manufacturing method.
SOLUTION: A silicon oxide film contains light-emitting nanosilicon having a particle size of 1.5 to 3.5 nm formed by a high-frequency sputtering method and a heat treatment, and is irradiated with ultraviolet light to emit blue, green, and red (light A white light-emitting silicon oxide film containing nanosilicon, which emits white light that is a combination of these three primary colors) clearly and stably, and is manufactured by a high-frequency sputtering method and a heat treatment method.
[Selection] Figure 4

Description

  The present invention relates to a nanosilicon-containing silicon oxide film that emits white light formed by combining three primary colors (red, green, and blue) of light by irradiation with ultraviolet light, and a method for producing the same.

  In the modern information society, demand for light-emitting diodes used for thin and light LCDs used in personal computers, TVs, car navigation systems, mobile phones, etc., as well as flashlights, interior lighting, and illumination is increasing day by day. ing. In the future, in order to further increase the added value of liquid crystal displays and light emitting diodes, several problems must be solved.

  In the liquid crystal display, improvement of the backlight light source is urgently required. The backlight light source emits light to the liquid crystal layer sandwiched between the glass substrates, and the liquid crystal layer displays the image by turning on and off the light. Therefore, the liquid crystal display requires a backlight light source. It is indispensable.

  However, the backlight light source requires high power consumption even in recent years when the demand for energy-saving products is increasing, and it is regarded as a problem that the backlight light source accounts for more than half of the power consumption of the liquid crystal display. Yes. Another problem is that a fluorescent tube enclosing mercury, which is an environmental pollutant, is used as a material for a backlight light source.

  On the other hand, in the light emitting diode, as in the case of the backlight light source, it is a problem that a material having a large global environmental load is used as a raw material. In addition, the sharpness of white color obtained from the white light emitting diode is a problem. In particular, white light-emitting diodes used in flashlights and the like are lacking in color clarity because a blue light-emitting diode is covered with a yellow filter to obtain white.

  In this way, the development of liquid crystal displays and light emitting diodes has so far been focused on increasing the screen size and brightness, but in the future, in addition to these points, the global environment, energy conservation, color It is necessary to promote development with more emphasis on the clarity of the image.

  The most suitable material for these requirements is nanosilicon. Nanosilicon is composed of silicon that has supported today's semiconductor industry, is a resource-rich, inexpensive, and particularly environmentally friendly material. Further, in terms of performance of a light-emitting element using nanosilicon as a light-emitting layer, it is possible to obtain red, green, and blue light emission with high luminance and long lifetime at a low driving voltage (see Non-Patent Documents 1 to 4).

  It is also possible to achieve white light emission by mixing red, green, and blue light emission colors (see Non-Patent Document 5). Nanosilicon is a liquid crystal display that takes into consideration the global environment and energy savings. It is promising as a useful material that can be used extensively as a backlight light source material and a new light source material that replaces white light emitting diodes.

  In addition, when nanosilicon is used as a backlight light source for liquid crystal displays, a structure in which nanosilicon is contained in a silicon oxide film of several tens of nanometers can be formed, so that a thinner and lighter liquid crystal display may be born. large.

  The color emanating from nanosilicon is determined by its particle size. That is, red emission is obtained from nanosilicon having a large particle size, and the emission color changes to blue as the particle size decreases.

  Therefore, in order to obtain white light emission more clearly, it is necessary to make the particle size of the nanosilicon light emitting mixed red, green, and blue (the three primary colors of light) uniform. In addition, in order to obtain a stable white light emission by mixing red, green, and blue light emission, it is necessary to uniformly disperse nanosilicon that emits light of each color in the silicon oxide film.

  In the prior art, a dry process method has been used to form nanosilicon in a silicon oxide film (see Patent Document 1). However, in this method, the manufacturing parameters for changing the particle size are complicated, and it is difficult to manufacture nanosilicon having a more uniform particle size in the silicon oxide film.

JP-A-7-237995 Proceedings of 21st Century Union Symposium (2002, Tokyo), p. 477-478 Proceedings of the 37th Annual Meeting of the Illuminating Society of Japan (August 4, 2004), p. 233, p. 234 Proceedings of the 51st Joint Conference on Applied Physics 3 (2004), 28p-P6-4 Tokai University Research Institute for Science and Technology Research Material Collection 24 (March 31, 2005), p. 40-46 Proceedings of the 52nd Joint Conference on Applied Physics No. 3 (March 29, 2005), p. 1641 (31p-YH-7)

  The production of nano-silicon-containing silicon oxide films that emit white light by mixing red, green, and blue light emissions is the development of a backlight light source for liquid crystal displays in consideration of the global environment, energy saving, and high definition. And promote the development of new white light sources to replace white light-emitting diodes.

  Therefore, the present invention provides: (i) white light emission in a state where nanosilicon that emits red, green, and blue light is contained in a silicon film; and (ii) white light emission is clearly and stably obtained. Let it be an issue (or purpose). Moreover, this invention makes it a subject (or objective) to establish the method of manufacturing (iii) the nano silicon containing silicon oxide film which light-emits white.

The inventor has conducted extensive research to solve the above problems,
(X) By adjusting the area ratio of the silicon chip and the quartz glass constituting the target material of the high-frequency sputtering method, the deposition conditions, and the heat treatment conditions, the particle size of the nanosilicon to be formed is between 1.5 and 3.5 nm. Controllable and
(Y) A clear and stable white light emission can be obtained from a silicon oxide film containing nanosilicon having a particle size of 1.5 to 3.5 nm.
I found.

  This invention was made | formed based on the said knowledge, and the summary is as follows.

  (1) The silicon oxide film contains light emitting nanosilicon having a particle size of 1.5 to 3.5 nm formed by high-frequency sputtering and heat treatment, and is irradiated with ultraviolet light to emit blue, green, and red (three primary colors of light). A white light-emitting silicon oxide film containing nanosilicon, which emits light in a clear and stable manner.

  (2) The light emitting nanosilicon is a blue light emitting nanosilicon having a particle size of 1.5 to 2.0 nm, a green light emitting nanosilicon having a particle size of 2.0 to 2.5 nm, and a red color having a particle size of 2.5 to 3.5 nm. The nano-silicon-containing white light-emitting silicon oxide film according to (1), which is made of light-emitting nano silicon.

  (3) The nanosilicon-containing white as described in (2) above, wherein the blue light-emitting nanosilicon, the green light-emitting nanosilicon, and the red light-emitting nanosilicon are formed in layers in the silicon oxide film. Luminescent silicon oxide film.

  (4) The nanosilicon-containing material according to (2), wherein the blue-emitting nanosilicon, the green-emitting nanosilicon, and the red-emitting nanosilicon are formed in the silicon oxide film in a mixed state. White light emitting silicon oxide film.

(5) In a method for producing a nano-silicon-containing white light-emitting silicon oxide film using high-frequency sputtering and heat treatment,
(I) Sputtering a target material in which silicon chips are arranged on quartz glass under the required sputtering conditions to form an amorphous silicon oxide film containing a predetermined amount of silicon atoms on the substrate;
(Ii) Heat-treating the amorphous silicon oxide film in an inert gas atmosphere to transform the film into a silicon oxide film and agglomerate silicon atoms to form light-emitting nanosilicon having a particle size of 1.5 to 3.5 nm. To
A method for producing a nano-silicon-containing white light-emitting silicon oxide film characterized in that

  (6) The nanosilicon-containing white light-emitting silicon oxide film according to (5), wherein an area ratio between a silicon chip and quartz glass on the target material is adjusted to control a particle size of the light-emitting nanosilicon. Production method.

  (7) The method for producing a nanosilicon-containing white light-emitting silicon oxide film according to (6), wherein an area ratio of the silicon chip to quartz glass is 1 to 50%.

  (8) The gas pressure and / or high-frequency power, which are the sputtering conditions, are adjusted to form red light emitting nanosilicon, green light emitting nanosilicon, and blue light emitting nanosilicon in layers. The manufacturing method of the nano silicon | silicone containing white light emission silicon oxide film in any one of-(7).

(9) The nanosilicon-containing white light-emitting oxidation according to (8), wherein the gas pressure is 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ torr and the high-frequency power is 10 to 500 W. A method for producing a silicon film.

  (10) The nanosilicon-containing white light-emitting oxidation according to any one of (5) to (9), wherein the temperature and / or time for the heat treatment is adjusted to control the particle size of the light-emitting nanosilicon. A method for producing a silicon film.

  (11) The method for producing a nano-silicon-containing white light-emitting silicon oxide film according to (10), wherein the temperature related to the heat treatment is 1000 to 1200 ° C. and the time is 15 to 100 minutes. .

  (12) The method for producing a nano-silicon-containing white light-emitting silicon oxide film according to (10), wherein the temperature related to the heat treatment is 900 to 1000 ° C. and the time is 10 to 60 minutes. .

  (13) The light emitting nanosilicon is a blue light emitting nanosilicon having a particle size of 1.5 to 2.0 nm, a green light emitting nanosilicon having a particle size of 2.0 to 2.5 nm, and a red having a particle size of 2.5 to 3.5 nm. The method for producing a nanosilicon-containing white light-emitting silicon oxide film according to any one of the above (5) to (12), which comprises light-emitting nanosilicon.

  ADVANTAGE OF THE INVENTION According to this invention, the white light emission silicon oxide film containing nano silicon of the particle size difficult to obtain by the conventional method can be manufactured, controlling the particle size of nano silicon.

  Nanosilicon is a material that is friendly to the global environment, and since the white light emitting silicon oxide film of the present invention provides clear and stable white light emission, the present invention provides a silicon oxide film containing nanosilicon. The use is expanded to the display field, lighting field, and other fields.

  First, an important point in the present invention will be briefly described. That is, a silicon oxide film containing nanosilicon that emits red, green, and blue light is produced, and a clear and stable white light emission obtained by mixing the three primary colors of light is obtained from the silicon oxide film.

  In order to achieve this, the nanosilicon-containing white light-emitting silicon oxide film of the present invention (the present silicon oxide film) is produced by the present invention production method (the present invention production method). Adopt high-frequency sputtering method and heat treatment process that can control the color).

First, an amorphous silicon oxide (SiO _x ) film is formed on a semiconductor substrate by high-frequency sputtering, and the amorphous silicon oxide film is subjected to heat treatment to form nanosilicon in the silicon oxide film.

  At this time, the particle size of the nanosilicon is the area ratio between the silicon chip and quartz glass constituting the target material in the high-frequency sputtering method, and the gas pressure that is the deposition condition (the gas pressure during production. In this manufacturing process, the argon gas ), High-frequency power, or heat treatment temperature and treatment time in the heat treatment process can be changed.

  The silicon oxide film of the present invention produced by this method emits white light by mixing red, green, and blue light emission, and thus lays the foundation for developing backlight light sources for liquid crystal displays and new white light source materials. .

  Below, the manufacturing process of this invention silicon oxide film is explained in full detail.

  The manufacturing method of the present invention includes a manufacturing method of forming each nanosilicon that emits red, green, and blue light in a layered manner by changing the area ratio or deposition condition of a silicon chip and quartz glass constituting a target material of a high-frequency sputtering method. There are two types of manufacturing methods that change the conditions of the heat treatment process and form each nanosilicon emitting red, green, and blue in a mixed state.

First, FIG. 1 shows an outline of the manufacturing process of the silicon oxide film of the present invention in which each nanosilicon emitting red, green and blue light is formed in layers. First, an amorphous silicon oxide (SiO _x ) film 3 in which silicon atoms 2 are mixed is formed on a semiconductor substrate 1 (silicon substrate or the like) by using a high-frequency sputtering method (see FIG. 5) (FIG. 1A, reference).

  Here, one mode of the high-frequency sputtering apparatus is shown in FIG. This apparatus is generally a vacuum chamber 16 having an argon gas introduction port 14 and an exhaust port 15 at the lower side of the side surface, and is attached to the upper surface of the vacuum chamber 16 via an insulating material 17 and introduced and discharged from a cooling pipe 18. A high-frequency electrode 22 having a substrate holder 20 cooled by 19 and a cathode shield 21 attached to the lower surface of the vacuum chamber 16 via an insulating material 17 and cooled by cooling water 19 introduced and discharged from the cooling pipe 18. It is composed of

  In the above apparatus, argon gas is introduced into the vacuum chamber 16 from the argon gas inlet 14, the argon gas is ionized by the high frequency controller 23, and the ionized argon ions are the target material 24 on the high frequency electrode 22. The silicon chip 24a and the quartz glass 24b (see FIG. 6, the silicon chips 24a are arranged on the quartz glass 24b vertically and horizontally at a predetermined interval) are caused to collide with each other.

Silicon atoms and silicon oxide molecules released from the target material 24 by this collision are deposited on the semiconductor substrate 1 held by the substrate holder 20 to form an amorphous silicon oxide (SiO _x ) film 3 mixed with silicon atoms 2. (See FIG. 1 (A)).

According to this high-frequency sputtering method, the nanosilicon particle size that directly contributes to the emission color can be controlled by adjusting the amount of silicon atoms 2 mixed into the amorphous silicon oxide (SiO _x ) film 3.

The amount of silicon atoms 2 mixed in the amorphous silicon oxide (SiO _x ) film 3 shown in FIG. 1 (A) is 5 to 10%, preferably 6 to 8%. Since red light emission is obtained from the amorphous silicon oxide (SiO _x ) film 3 containing this amount of silicon atoms 2, this film layer is referred to as a red light emitting layer 4.

  The amount of silicon atoms 2 can be adjusted by changing the area ratio between the silicon chip 24a and the quartz glass 24b (see FIG. 6) constituting the target material 24.

That is, by changing the amount of silicon atoms released from the target material 24 due to the difference in area between the silicon chip 24 a and the quartz glass 24 b, the amorphous silicon oxide (SiO _x ) film 3 deposited on the semiconductor substrate 1 is changed. The amount of silicon atoms 2 mixed in can be freely adjusted. The area ratio is usually 25 to 50%, preferably 30%.

  Also, the amount of silicon atoms 2 can be adjusted by changing the deposition conditions such as gas pressure and high frequency power.

  This is because plasma (playing argon gas introduced into the vacuum chamber 16 is played by the high-frequency controller 23) that plays an important role in the release of silicon atoms and silicon oxide molecules from the target material 24 by changing the gas pressure and high-frequency power. This is because the density of the state ionized by argon ions and electrons (see FIG. 5) can be freely changed.

  In the manufacturing process of the present invention, using this plasma phenomenon, argon ions having a positive charge are charged into the target material 24 that is negatively charged by electrons (because electrons have a higher mobility than argon ions). Colliding to release silicon atoms and silicon oxide molecules from the target material 24.

That is, since the rate ratio of silicon atoms and silicon oxide molecules released from the target material 24 varies depending on the gas pressure and high frequency power, the amount of silicon atoms released from the target material 24 by changing the gas pressure and high frequency power. As a result, the amount of silicon atoms 2 mixed in the amorphous silicon oxide (SiO _x ) film 3 deposited on the semiconductor substrate 1 can be controlled.

At this time, the gas pressure is 1 × 10 ^{−4 to} 5 × 10 ⁻³ torr, preferably 1 × 10 ⁻³ torr. Moreover, although the high frequency electric power value shall be 150-500W, Preferably it is 200W. And the deposition time at the time of forming the red light emitting layer 4 is 10 to 60 minutes, Preferably it is 15 to 50 minutes, More preferably, it is 30 to 40 minutes.

Next, an amorphous silicon oxide (SiO _x ) film 3 in which the amount of silicon atoms 2 is reduced is formed on the red light emitting layer 4 shown in FIG. 1A (see FIG. 1B). At this time, the mixing amount of silicon atoms 2 is 2 to 5%, preferably 3%.

Green light emission can be obtained from the amorphous silicon oxide (SiO _x ) film 3 containing this amount of silicon atoms 2, and this film layer is referred to as a green light emitting layer 5.

The area ratio between the silicon chip 24a and the quartz glass 24b when the green light emitting layer 5 is formed is usually 10 to 25%, preferably 20%. The gas pressure is set to 1 × 10 ⁻³ to 1 × 10 ⁻² torr, preferably 5 × 10 ⁻³ torr.

  Furthermore, the high frequency power value is 75 to 150 W, preferably 100 W. And the deposition time at the time of forming the green light emitting layer 5 is 10 to 60 minutes, Preferably it is 15 to 50 minutes, More preferably, it is 30 to 40 minutes.

Next, an amorphous silicon oxide (SiO _x ) film 3 in which the amount of mixed silicon atoms 2 is further reduced is formed on the red light emitting layer 4 / green light emitting layer 5 shown in FIG. 1B (FIG. 1C). ,reference). The amount of silicon atoms 2 mixed at this time is 0.5 to 2%, preferably 1%. Blue light emission can be obtained from the amorphous silicon oxide (SiO _x ) film 3 containing this amount of silicon atoms 2, and this film layer is referred to as a blue light emitting layer 6.

The area ratio between the silicon chip 24a and the quartz glass 24b when forming the blue light emitting layer 6 is normally 1 to 10%, preferably 5%. The gas pressure is 5 × 10 ⁻³ to 1 × 10 ⁻¹ torr, preferably 1 × 10 ⁻² torr. Further, the high-frequency power value is 10 to 75 W, preferably 50 W.

  And the deposition time at the time of forming the blue light emitting layer 6 is 10 to 60 minutes, Preferably it is 15 to 50 minutes, More preferably, it is 30 to 40 minutes.

Next, the amorphous silicon oxide (SiO _x ) film 3 is heat-treated 7 in an atmosphere of an inert gas (argon, helium, etc.) to transform the amorphous silicon oxide (SiO _x ) film 3 into a silicon oxide film 9.

In the middle stage of the heat treatment 7, the silicon atoms 2 mixed in the amorphous silicon oxide (SiO _x ) film 3 begin to move violently in the silicon oxide film 9, and the silicon atoms 2 gradually aggregate. Thus, a large number of stable nanosilicones 8 having a predetermined particle size are formed in each light emitting layer (see FIG. 1D).

  Through such a manufacturing process, nanosilicones having a predetermined particle size are distributed in layers, and the nanosilicon-containing silicon oxide film 10 having the red light emitting layer 4, the green light emitting layer 5, and the blue light emitting layer 6 can be manufactured. .

  And about the particle size of the nano silicon 8 in each light emitting layer, the particle size of the nano silicon in the red light emitting layer 4 is 2.5-3.5 nm, and the particle size of the nano silicon in the green light emitting layer 5 is 2. The particle size of nano silicon in the blue light emitting layer 6 is 1.5 to 2.0 nm.

  Moreover, in the case of the said heat processing 7, although the heat processing temperature shall be 1000-1200 degreeC, Preferably it is 1050-1100 degreeC. Further, the heat treatment time is 15 to 100 minutes, preferably 30 to 80 minutes, and more preferably 50 to 60 minutes.

  Next, an outline of a manufacturing method for manufacturing the silicon oxide film of the present invention by changing the conditions of the heat treatment process will be described.

  FIG. 2 shows a manufacturing process for manufacturing the silicon oxide film of the present invention in which issued nanosilicon having a predetermined particle size is mixed by a heat treatment process. Also in the production of the silicon oxide film of the present invention by a heat treatment process, a high frequency sputtering method capable of freely controlling the nanosilicon particle size is employed.

FIG. 2A shows an amorphous silicon oxide (SiO _x ) film 3 in which a large amount of silicon atoms 2 are mixed on the semiconductor substrate 1 in accordance with the above manufacturing process. At this time, the mixing amount of the silicon atoms 2 is set to 5 to 10%, preferably 6 to 8%.

When the amorphous silicon oxide (SiO _x ) film 3 is formed, the area ratio between the silicon chip 24a and the quartz glass 24b is usually 25 to 50%, preferably 30%.

The gas pressure is 1 × 10 ^{−4 to} 5 × 10 ⁻³ torr, and preferably 1 × 10 ⁻³ torr. Furthermore, the high-frequency power value is 150 to 500 W, preferably 200 W.

The deposition time for forming the amorphous silicon oxide (SiO _x ) film 3 is 10 to 120 minutes, preferably 30 to 100 minutes, and more preferably 50 to 60 minutes.

Next, the amorphous silicon oxide (SiO _x ) film 3 is heat-treated 7 in an atmosphere of an inert gas (argon, helium, etc.) to emit light in blue, green, and red in the silicon oxide film 9, respectively. A large number of nanosilicones having a particle size to be formed are formed (see FIG. 2B).

  Regarding the particle size of the nanosilicon formed at this time, the particle size of the blue light emitting nanosilicon 11 is 1.5 to 2.0 nm, and the particle size of the green light emitting nanosilicon 12 is 2.0 to 2.5 nm. The particle size of the red light emitting nanosilicon 13 is 2.5 to 3.5 nm.

  The particle size of the nanosilicon can be freely adjusted by changing the heat treatment temperature in the manufacturing process. That is, nanosilicon having a relatively stable particle size is formed at a heat treatment temperature of 1000 ° C. or higher. However, when the heat treatment temperature is set to 1000 ° C. or less, the formation of nanosilicon becomes unstable, and eventually the particle size becomes nonuniform.

  Therefore, by performing heat treatment at 1000 ° C. or less, light-emitting nanosilicon having various sizes from a large particle size to a small particle size can be formed and mixed in the silicon oxide film. For this reason, during the heat treatment 7, the heat treatment temperature is set to 900 to 1000 ° C, preferably 920 to 980 ° C.

Even if the heat treatment time is changed, the nanosilicon particle size can be controlled. The particle size of the nanosilicon is determined by the amount of aggregation of silicon atoms 2 in the amorphous silicon oxide (SiO _x ) film 3 generated in the heat treatment process. This is because the amount of aggregation of silicon atoms 2 directly corresponds to the amount of silicon atoms constituting nanosilicon.

  From this, it becomes possible to adjust the amount of aggregation of the silicon atoms 2 by changing the heat treatment time, and the particle size of the nanosilicon can be controlled. The heat treatment time is usually 10 to 60 minutes, preferably 20 to 40 minutes, and more preferably 30 minutes.

  Through such a manufacturing process, the nanosilicon-containing silicon oxide film 10 containing the blue-emitting nanosilicon 11, the green-emitting nanosilicon 12, and the red-emitting nanosilicon 13 in a mixed state can be manufactured.

  Here, a transmission electron micrograph of nanosilicon produced by the above production method is shown in FIG. The circled portion in the figure is nanosilicon. FIG. 3 shows that nanosilicon is uniformly dispersed in the silicon oxide film and exists in a spherical shape. The nanosilicon particle size is in the range of 1.5 to 3.5 nm.

  Next, FIG. 4 shows an emission spectrum of the silicon oxide film of the present invention. From FIG. 4, white light emission having a very broad peak band can be obtained from the silicon oxide film of the present invention over a wavelength range of 400 nm to 800 nm.

  In the case of the silicon oxide film of the present invention in which nanosilicon is distributed in a layered manner to form a light emitting layer, this white light emission is emitted from nanosilicon existing in each light emitting layer, that is, red, green, and blue light are mixed. It was obtained.

  In addition, in the case of the silicon oxide film of the present invention containing the nano-silicon of various particle sizes in a mixed state, the white light emission is a red light-emitting nano silicon, a green light-emitting nano silicon, which are uniformly dispersed in the silicon oxide film, and The light emission of each color from the blue-emitting nanosilicon is mixed and obtained.

  The luminance of white light emission obtained with the silicon oxide film of the present invention is very strong when irradiated with ultraviolet light, and can be clearly observed with the naked eye under room lighting. Furthermore, the white light emission obtained by the silicon oxide film of the present invention has a long light emission lifetime and is stable.

  Thus, according to the manufacturing method of the present invention, a silicon oxide film containing nanosilicon containing the silicon oxide film according to the present invention (the present invention silicon oxide) is vividly and stably emitting white light and is friendly to the global environment (non-toxic and harmless). Membrane) can be produced.

  The silicon oxide film of the present invention can be used as a useful material for a backlight light source for liquid crystal displays and a novel white light source replacing a white light emitting diode in the display field, lighting field, etc. by actively utilizing the light emission characteristics. .

  As described above, nanosilicon is gentle to the global environment (non-toxic and harmless), and the silicon oxide film of the present invention containing nanosilicon having a uniform particle size emits a bright and stable white light. Expands the use of nanosilicon-containing silicon oxide films to the display field, lighting field, and other fields.

  For example, the present invention enables commercialization of a backlight light source for liquid crystal displays and a new white light source that replaces white light emitting diodes. As described above, the present invention is highly likely to be used for the development of a technology for commercializing an innovative white light source of the 21st century in the display field, lighting field, and other fields.

It is a figure which shows the process in which the nano silicon containing white light emission silicon oxide film of this invention is manufactured. (A) is a figure which shows the aspect which formed the red light emitting layer, (B) is a figure which shows the aspect which formed the green light emitting layer on the red light emitting layer, (C) is on a green light emitting layer. It is a figure which shows the aspect which formed the blue light emitting layer in (D), and is a figure which shows the aspect of the nano silicon containing silicon oxide film in each light emitting layer. It is a figure which shows another process of manufacturing the nano silicon containing white light emission silicon oxide film of this invention. (A) is a diagram showing an embodiment of the amorphous silicon oxide (SiO _x) film containing silicon atoms, the embodiment of (B) is blue, green, nano silicon-containing white light-emitting silicon oxide film that emits red light FIG. It is a figure (transmission electron micrograph) which shows the nanosilicon presence aspect in the nanosilicon containing white light emission silicon oxide film of this invention. It is a figure which shows the emission spectrum of the nano silicon containing white silicon oxide film of this invention. It is a figure which shows the one aspect | mode of the high frequency sputtering device used with the manufacturing method of this invention. It is a figure which shows the aspect of the target material used in a high frequency sputtering device.

Explanation of symbols

1 semiconductor substrate 2 silicon atoms 3 amorphous silicon oxide (SiO _x) film 4 red light emitting layer 5 green light-emitting layer 6 blue light-emitting layer 7 heat treatment 8 Nanosilicon 9 silicon oxide film 10 nano silicon-containing silicon oxide film 11 blue light emitting nano silicon 12 green Light emitting nano silicon 13 Red light emitting nano silicon 14 Argon gas inlet 15 Exhaust 16 Vacuum chamber 17 Insulating material 18 Cooling tube 19 Cooling water 20 Substrate holder 21 Cathode shield 22 High frequency electrode 23 High frequency controller 24 Target material 24a Silicon chip 24b Quartz glass

Claims (13)

  The silicon oxide film contains light-emitting nanosilicon with a particle size of 1.5 to 3.5 nm formed by high-frequency sputtering and heat treatment, and combined with blue, green, and red (the three primary colors of light) by ultraviolet light irradiation. A nano-silicon-containing white light-emitting silicon oxide film, which emits bright white light clearly and stably.   The light emitting nanosilicon is a blue light emitting nanosilicon having a particle size of 1.5 to 2.0 nm, a green light emitting nanosilicon having a particle size of 2.0 to 2.5 nm, and a red light emitting nanosilicon having a particle size of 2.5 to 3.5 nm. The nanosilicon-containing white light-emitting silicon oxide film according to claim 1, comprising:   3. The nano-silicon-containing white light-emitting silicon oxide film according to claim 2, wherein the blue light-emitting nanosilicon, the green light-emitting nanosilicon, and the red light-emitting nanosilicon are formed in layers in the silicon oxide film. .   3. The nanosilicon-containing white light emitting silicon oxide according to claim 2, wherein the blue light emitting nanosilicon, the green light emitting nanosilicon, and the red light emitting nanosilicon are formed in a mixed state in the silicon oxide film. film. In a method for producing a nano-silicon-containing white light-emitting silicon oxide film using high-frequency sputtering and heat treatment,
(I) Sputtering a target material in which silicon chips are arranged on quartz glass under the required sputtering conditions to form an amorphous silicon oxide film containing a predetermined amount of silicon atoms on the substrate;
(Ii) Heat-treating the amorphous silicon oxide film in an inert gas atmosphere to transform the film into a silicon oxide film and agglomerate silicon atoms to form light-emitting nanosilicon having a particle size of 1.5 to 3.5 nm. To
A method for producing a nano-silicon-containing white light-emitting silicon oxide film characterized in that   The method for producing a nano-silicon-containing white light-emitting silicon oxide film according to claim 5, wherein the particle size of the light-emitting nano silicon is controlled by adjusting an area ratio between the silicon chip and the quartz glass on the target material.   The method for producing a nano-silicon-containing white light-emitting silicon oxide film according to claim 6, wherein an area ratio of the silicon chip to quartz glass is 1 to 50%.   The gas pressure and / or high-frequency power, which are the sputtering conditions, are adjusted to form red light emitting nanosilicon, green light emitting nanosilicon, and blue light emitting nanosilicon in layers. A method for producing a nano-silicon-containing white light-emitting silicon oxide film according to claim 1. 9. The production of nano-silicon-containing white light emitting silicon oxide film according to claim 8, wherein the gas pressure is 1 * 10 < ^-4 > to 1 * 10 < ^-1 > torr and the high frequency power is 10 to 500 W. Method.   The production of a nano-silicon-containing white light-emitting silicon oxide film according to any one of claims 5 to 9, wherein a particle size of the light-emitting nano silicon is controlled by adjusting a temperature and / or time related to the heat treatment. Method.   11. The method for producing a nanosilicon-containing white light-emitting silicon oxide film according to claim 10, wherein a temperature related to the heat treatment is 1000 to 1200 ° C. and the time is 15 to 100 minutes.   The method for producing a nanosilicon-containing white light-emitting silicon oxide film according to claim 10, wherein a temperature related to the heat treatment is 900 to 1000 ° C. and the time is 10 to 60 minutes.   The light emitting nanosilicon is a blue light emitting nanosilicon having a particle size of 1.5 to 2.0 nm, a green light emitting nanosilicon having a particle size of 2.0 to 2.5 nm, and a red light emitting nanosilicon having a particle size of 2.5 to 3.5 nm. The method for producing a nanosilicon-containing white light-emitting silicon oxide film according to any one of claims 5 to 12, wherein the method comprises: