JP4929469B2 - Light emitting element manufacturing method using compound containing Si-O-Si bond - Google Patents

Description

  The present invention relates to a method for manufacturing a light emitting device, and in particular, a Si—O—Si bond for forming a light emitting modified layer that emits a desired color by irradiating a compound containing a Si—O—Si bond with predetermined light. The present invention relates to a method for manufacturing a light-emitting element using a compound containing.

  In the field of optoelectronics, photonics or bio / medical, light emitting devices are indispensable. Currently, light emitting devices are often formed on rigid substrates such as silicon and silica glass. This has limited the use of the device in terms of lightness, impact resistance, weather resistance, flexibility, and the like. Further, the emission wavelength of the element is also limited by the material, and it has been difficult to obtain a desired color from one kind of material.

  Si-O-Si bonds that are not limited to rigid substrates are formed by selectively or spatially forming a light emitting modified layer that emits a desired color on the surface or inside of a compound containing Si-O-Si bonds. It is an object to establish a method for manufacturing a novel light-emitting element based on a compound containing benzene.

  Therefore, in view of the above points, the present invention provides a compound containing a Si—O—Si bond that can form a light emitting modified layer emitting a desired color on the surface or inside of the compound containing a Si—O—Si bond. It is an object to provide a method for manufacturing a light-emitting element using the material.

  Other objects and novel features of the present invention will be clarified in embodiments described later.

In order to achieve the above object, a method for manufacturing a light-emitting element using a compound including a Si—O—Si bond according to the first aspect of the present invention includes the surface of a compound including a Si—O—Si bond or the inside thereof. Irradiation with a first light having a wavelength of 190 nm or more and less than 266 nm, and then irradiation of the exposed compound with a second light having a wavelength of 190 nm or more and less than 266 nm in a vacuum enhances the reduction reaction and emits a desired color. It is characterized by forming a light emitting modified layer.

The light emitting element manufacturing method using the compound containing Si—O—Si bond according to the second aspect of the present invention is the first having a wavelength of 190 nm or more and less than 266 nm on the surface or inside of the compound containing Si—O—Si bond. After that, the exposed compound is irradiated with a second light having a wavelength shorter than that of the first light and a wavelength of 190 nm or less in a gas mixture containing oxygen to enhance the oxidation reaction. It is characterized by forming a light-emitting modified layer that emits the above-mentioned color.

In the method for manufacturing a light-emitting element using a compound including a Si—O—Si bond according to the third aspect of the present invention, light having a wavelength of 190 nm or more and less than 266 nm is applied to the surface or inside of the compound including a Si—O—Si bond. The irradiated and exposed compound is then subjected to a heat treatment in a gas mixture containing oxygen to enhance the oxidation reaction, thereby forming a light emitting modified layer that emits a desired color.

  It should be noted that any combination of the above components is also effective as an aspect of the present invention.

  According to the present invention, a Si—O—Si bond that is not limited to a rigid substrate is formed by forming a light emitting modified layer that emits a desired color on the surface or inside of a compound that contains a Si—O—Si bond. Necessary for the fabrication of multifunctional micro / nano-sized devices such as compound light-emitting device fabrication methods that can be established and used as basic technology for device fabrication in optoelectronics, photonics or bio / medical fields It becomes an indispensable technology. The present invention is not limited to these fields, and can be used greatly in the field of device fabrication that will be developed using micro / nanomachining technology.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a configuration diagram illustrating a light-emitting element manufacturing method using a compound including a Si—O—Si bond according to the present invention, in which (A) is Embodiment 1 and (B) is a configuration diagram illustrating Embodiment 2. FIG. is there. In the Example of this invention, it is a graph which shows the change of the emission spectrum of the modification layer in various modification conditions. It is a photograph figure which shows the change of the luminescent color of the modification | reformation sample surface in various modification conditions (the lower table of FIG. 2). It is the photograph figure which prototyped various light-guide plates in various modification conditions (the lower table of FIG. 2).

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In addition, the same code | symbol is attached | subjected to the same or equivalent component, member, process, etc. which are shown by each drawing, and the overlapping description is abbreviate | omitted suitably. In addition, the embodiments do not limit the invention but are exemplifications, and all features and combinations thereof described in the embodiments are not necessarily essential to the invention.

  FIG. 1 illustrates an embodiment of a method for manufacturing a light-emitting element of a compound including a Si—O—Si bond according to the present invention. FIG. 1A is a schematic configuration of an experiment used in Embodiment 1 in the case where a light-emitting modified layer is formed on the surface of a solid organic polysiloxane as a compound containing a Si—O—Si bond. Silicone 1 has a mask 3 disposed on the surface, and laser light 2 having a wavelength of 190 nm or more and less than 266 nm is irradiated to the surface of the solid organic polysiloxane 1 through the mask 3.

  A light emitting modified layer is formed on the surface of the solid organic polysiloxane 1 irradiated with light through the opening of the mask 3. The light emitting modified layer is made of silicon oxide but not in stoichiometric composition (not silicon dioxide).

  When the wavelength of the laser beam to be irradiated is less than 190 nm, silicon dioxide having a stoichiometric composition is mainly formed as a modified layer and the light emitting property is lost. Therefore, the laser beam to be irradiated needs to be 190 nm or more. In addition, irradiation with a laser beam of 266 nm or more causes carbon to be deposited, and a light emitting modified layer cannot be obtained.

  By controlling the balance between enhancement and suppression of the oxidation / reduction reaction induced when the laser beam 2 having a wavelength of 190 nm or more and less than 266 nm is irradiated, a light emitting modified layer emitting a desired color can be obtained. For example, by changing the atmosphere in which the solid organic polysiloxane 1 is installed at the time of laser light irradiation to vacuum, air, or an oxygen gas atmosphere having a higher concentration than oxygen contained in the air, The color can be changed, and when the oxygen concentration increases, the emission peak wavelength tends to shift to the longer wavelength side.

  Further, the color of the light emitting modified layer also changes depending on the atmosphere in which the solid organic polysiloxane 1 is placed before laser light irradiation. For example, the emission peak wavelength tends to shift to the shorter wavelength side as the time during which the solid organic polysiloxane 1 is placed in the vacuum before the laser light irradiation becomes longer.

  When the solid organic polysiloxane 1 is irradiated with laser light 2 having a wavelength of 190 nm or more and less than 266 nm to the solid organic polysiloxane 1 in the atmosphere (or a mixture containing oxygen), a light emitting modified layer is formed. In addition, the color of the light emitting modified layer can be changed by irradiating laser light having a wavelength of 190 nm or more and less than 266 nm (may be the same wavelength or different wavelengths) in a vacuum. That is, the emission peak wavelength can be shifted to the short wavelength side. Laser irradiation in vacuum in the post-process corresponds to enhancement of the reduction reaction.

  In addition, when the light-emitting modified layer is formed by irradiating the solid organic polysiloxane 1 with laser light 2 having a wavelength of 190 nm or more and less than 266 nm in the atmosphere (or a mixture containing oxygen), a sample in which the light-emitting modified layer is formed On the other hand, the color of the light emitting modified layer can be changed by irradiating a laser beam having a wavelength of 190 nm or less (shorter wavelength than the laser beam initially irradiated) in the atmosphere (or a mixture containing oxygen). . That is, the emission peak wavelength can be shifted to the long wavelength side. Laser irradiation in the air (or a mixture containing oxygen) in the subsequent process corresponds to enhancement of the oxidation reaction.

  Further, when a light emitting modified layer is formed by irradiating the solid organic polysiloxane 1 with laser light 2 having a wavelength of 190 nm or more and less than 266 nm in oxygen gas (or a mixture containing oxygen) at 1 atm, the light emitting modified layer is formed. The color of the light emitting modified layer can be changed by heat-treating the sample in which the film is formed in the same atmosphere. That is, the emission peak wavelength can be shifted to the long wavelength side. The heat treatment in the oxygen-containing atmosphere in the post process corresponds to enhancement of the oxidation reaction.

  According to the first embodiment, the following effects can be obtained.

(1) By irradiating the solid organic polysiloxane 1 with the laser beam 2 through the mask 3, the light emission modified layer can be formed in a position-selective manner. That is, by using the mask 3 having a desired opening shape, the light emitting modified layer having a desired shape and size defined by the opening shape and size is formed at a desired position defined by the opening position. It can be formed on the surface of the solid organic polysiloxane 1.

(2) By controlling the balance between enhancement and suppression of oxidation / reduction reactions induced when irradiating laser light 2 having a wavelength of 190 nm or more and less than 266 nm, a light emitting modified layer that emits a desired color can be obtained. .

(3) By adopting a material such as flexible silicone rubber as the solid organic polysiloxane 1 on which the light emitting modified layer is provided, a flexible light emitting device in which a light emitting material is formed can be produced.

  FIG. 1B is a schematic configuration of an experiment used in Embodiment 2 in the case where a light emitting modified layer is formed on the surface of a solid organic polysiloxane as a compound containing a Si—O—Si bond. (Silicon) 1 is irradiated with a laser beam 2 having a wavelength of 190 nm or more and less than 266 nm through a lens 4 as an optical element.

  In this case, the solid organic polysiloxane 1 can be finely moved in a three-dimensional manner, and as a result, the laser beam 2 is scanned in a three-dimensional manner.

  Also in the second embodiment, the color of the light emitting modified layer can be changed by the same method as listed in the first embodiment.

  According to the second embodiment, the light emitting modified portion is formed in a position-selective manner and a space-selective manner (three-dimensionally) by adjusting the focal position of the laser light 2 inside the solid organic polysiloxane 1. Can do. Other functions and effects are the same as those of the first embodiment.

  In FIG. 1B, a light emission modified layer having a desired shape and size may be formed at a desired position on the surface of the silicone 1 by adjusting the focal position of the laser beam 2 to the surface of the silicone 1. it can.

  In FIGS. 1A and 1B, the solid organic polysiloxane 1 is irradiated with laser light having a wavelength of 190 nm or more and less than 266 nm, but is not limited to laser light. An ArF excimer laser or a KrF excimer laser can be used as a light source for generating laser light having a wavelength of 190 nm or more and less than 266 nm.

[Example]
Hereinafter, the light emitting element manufacturing method using the compound containing the Si-O-Si bond concerning this invention is explained in full detail in an Example.

Silicone rubber as a compound containing a Si—O—Si bond is placed in a vacuum chamber, the evacuation time is changed from 0 to 72 hours, and the amount of oxygen gas molecules contained in the silicone rubber is qualitatively determined. Four types of samples were prepared with changes. At this time, ArF excimer laser light having a wavelength of 193 nm was used as the laser light. The irradiation conditions of ArF excimer laser light were a fluence (energy density) of 40 mJ / cm ² , an irradiation time of 20 minutes, and a repetition frequency of 10 Hz.

  The sample that had been evacuated for 0 hour, that is, modified in the air, showed a broad emission spectrum having a peak at 435 nm. On the other hand, emission spectra having a peak at 400 nm were obtained for the samples with evacuation times of 3, 30 and 72 hours. Further, when the relationship between the evacuation time and the emission intensity at an emission wavelength of 400 nm was plotted, it was found that the emission intensity became stronger as the sample was degassed for a longer time in the range of the evacuation time from 0 to 72 hours. In addition, when the peak intensity of the emission spectrum of the modified sample with a evacuation time of 3 to 72 hours was normalized, it was found that when the evacuation time was increased, the spectrum had a shoulder near 460 nm. Therefore, when the modified atmosphere is evacuated, it changes to blue light emission having a peak at a wavelength of 400 nm, and the spectrum becomes sharpest when the evacuation time is 3 hours, and the intensity is strongest at 72 hours. I found out that

It has been found that the emission spectrum changes when the sample modified in the atmosphere is further placed in a vacuum and irradiated again with ArF excimer laser light. First, the surface of the silicone rubber was irradiated with ArF excimer laser light at a fluence of 40 mJ / cm ² , 20 minutes at the time of irradiation, and a repetition frequency of 10 Hz. This modified sample was placed in a vacuum chamber and evacuated for 72 hours to remove oxygen gas molecules inside and outside the silicone rubber, and then the irradiation time of ArF excimer laser light was changed from 10 to 60 minutes. ArF excimer laser light irradiation in vacuum was also performed under conditions of a fluence of 40 mJ / cm ² and a repetition frequency of 10 Hz. Compared with the sample before irradiation with ArF excimer laser light in vacuum, the sample irradiated with ArF excimer laser light in vacuum had a weak emission intensity in the vicinity of 500 to 700 nm. On the other hand, the intensity around 400 to 450 nm became strong. Further, it was found that the change in the emission spectrum with respect to the irradiation time of the laser beam was remarkable during the irradiation time from 0 to 10 minutes, but was almost saturated after that. Therefore, by irradiating the sample modified in the atmosphere with ArF excimer laser light again in vacuum, the modified layer shows blue light emission having a peak at 405 nm, and its spectral intensity is 10 minutes of laser light irradiation time. It was found to be saturated.

The change in the emission spectrum was also found by irradiating the modified sample with F ₂ laser light in N ₂ / O ₂ (mixture of nitrogen gas and oxygen gas). Silicone rubber was irradiated with ArF excimer laser light (fluence 40 mJ / cm ² , irradiation time 20 minutes, repetition frequency 10 Hz), and then F ₂ laser light (wavelength 157 nm) was changed from irradiation time 10 to 120 minutes. The irradiation conditions of the F ₂ laser light at that time were set to a fluence of 10 mJ / cm ² and a repetition frequency of 10 Hz constant. When irradiated with F ₂ laser light, the emission intensity in the vicinity of 500 to 650 nm became stronger only at 10 minutes. On the other hand, at the irradiation time of 20 minutes and 40 minutes, the intensity gradually decreased, and almost no change in intensity was observed after 60 minutes. At the time of this intensity change, it was found that the peak wavelength shifted to the longer wavelength side as the F ₂ laser light irradiation time became longer.

The reforming atmosphere was oxygen gas at 1 atm, and irradiation with ArF excimer laser light was performed. At that time, the irradiation time was changed from 20 to 60 minutes. The fluence and pulse repetition frequency were fixed at 40 mJ / cm ² and 10 Hz, respectively. When the laser beam irradiation time was 30 minutes, the emission intensity became the strongest. In addition, the emission peak position of the sample modified in oxygen gas changed to a longer wavelength side than the sample modified in the air. From this, it has been found that it is effective to use a high-concentration oxygen gas in the modified atmosphere in order to broaden the emission spectrum of the modified sample to the long wavelength side.

The effect of heat-treating a sample that was modified with ArF excimer laser (fluence 40 mJ / cm ² , irradiation time 30 minutes, pulse repetition frequency 10 Hz) in the oxygen gas was examined. When the heat treatment temperature was 300 ° C., the emission peak wavelength shifted to the long wavelength side at 483 nm, and an emission spectrum having a yellow color was obtained.

Up to now, it has been found that a light emitting modified layer emitting various visible lights from blue to yellow can be formed by changing the processing conditions of the modified layer and the forming conditions of the modified layer. The main conditions found experimentally to date are summarized in the table below in FIG. The emission spectrum of the sample modified under the conditions of # 1 to # 6 is shown in the upper graph of FIG. FIG. 3 shows the state of light emission when these modified samples (1 cm × 1 cm) are excited with a He—Cd laser beam having a wavelength of 325 nm. In FIG. 3A, the emission intensity and emission wavelength are uneven due to some nonuniformity of the modified portion due to the intensity distribution of the laser beam. Therefore, the photograph which cut out the center part (center part of a laser beam irradiation area | region) of the modified surface by 3 mm x 3 mm was added to FIG.3 (b). As shown in the lower table of FIG. 2, # 1 is a sample modified in vacuum, # 3 in the atmosphere, and # 5 in oxygen gas. # 2, # 4, the sample # 3 was modified in the air, respectively reduced using ArF excimer laser or F ₂ laser, a sample oxidation. # 6 is a sample obtained by further heat-treating the sample of # 5 modified in oxygen.

  A feature of the emission spectrum of # 1 is that it shows the sharpest blue emission having a peak wavelength at 400 nm.

  The characteristic of the emission spectrum of # 2 is that it has a peak wavelength at 405 nm and emits light in a broader wavelength range than # 1, which shows the same blue light emission, and therefore shows pale light emission.

  The feature of the # 3 emission spectrum is that it has a peak wavelength at 435 nm and emits white light with little blue. Moreover, since it is obtained by irradiating ArF excimer laser light in the atmosphere, it is the simplest method.

  The characteristic of the emission spectrum of # 4 has a peak wavelength at 440 nm and shows white emission with little blue as in # 3. Only the emission center on the short wavelength side of the emission spectrum of the sample # 3 was decreased, and the emission center was shifted to the long wavelength side.

  The feature of the emission spectrum of # 5 is that it has a peak wavelength at 460 nm and shows brighter white light emission.

  The feature of # 6 emission spectrum is that it has a peak wavelength at 483 nm and emits yellowish white light.

  By changing the sample formation conditions as in # 1 to # 6, light emitting layers having different spectra from blue light emission having a peak at 400 nm to yellowish white light emission having a peak at 483 nm could be formed.

  A copper mask shaped like a character (character range 10 mm x 20 mm) is placed on a sheet-like silicone rubber with a thickness of 0.2 mm, and # 1 (in vacuum) and # 3 (in air) in the lower table of FIG. And # 5 (in oxygen). FIG. 4 shows the state of light emission when this sample is irradiated with a He—Cd laser beam having a wavelength of 325 nm. It can be seen that the laser exposure part shaped like a letter emits light. Also, the emission spectra differed depending on the modified atmosphere, with blue emission at # 1, blue white emission at # 3, and brighter white emission at # 5.

  Although the embodiments and examples of the present invention have been described above, it is obvious to those skilled in the art that the present invention is not limited thereto and various modifications and changes can be made within the scope of the claims. I will.

1 Fixed organic polysiloxane 2 Laser light 3 Mask 4 Lens

Claims (3)

The surface or inside of the compound containing a Si—O—Si bond is irradiated with a first light having a wavelength of 190 nm or more and less than 266 nm, and then the exposed compound is exposed to a second light having a wavelength of 190 nm or more and less than 266 nm in a vacuum. A method for producing a light-emitting element using a compound containing a Si—O—Si bond, which forms a light-emitting modified layer that emits a desired color by irradiating the compound with a reduction reaction . The surface or the inside of the compound containing a Si—O—Si bond is irradiated with a first light having a wavelength of 190 nm or more and less than 266 nm, and then the exposed compound is exposed to the first light in a gas mixture containing oxygen. A compound containing a Si—O—Si bond, characterized in that a second light having a wavelength of 190 nm or less is irradiated at a short wavelength to enhance the oxidation reaction and form a light emitting modified layer that emits a desired color. A light emitting element manufacturing method. Irradiating light having a wavelength of 190 nm or more and less than 266 nm to the surface or inside of a compound containing a Si—O—Si bond, and then subjecting the exposed compound to heat treatment in a gas mixture containing oxygen to enhance the oxidation reaction A method for manufacturing a light-emitting element using a compound including a Si—O—Si bond, wherein a light-emitting modified layer that emits a desired color is formed.