InP-phthalocyanine composite material and preparation method thereof

Abstract

The invention provides an InP-phthalocyanine composite material and a preparation method thereof. According to the InP-phthalocyanine composite material prepared through a double-temperature-zone chemical vapor deposition method, InP is of a nano-particle structure, phthalocyanine is dispersed in the InP, phthalocyanine molecules are not prone to forming dimers, the prepared composite material has good optical limiting capacity, the preparation technology is simple, and the reaction process is easy to control. Experiments show that the linear transmittance of the composite material is 80%, the output amplitude is 0.76 J / cm < 2 >, the nonlinear limit transmittance is 4.75%, the NAF value is 16.8, and the nonlinear attenuation rate is about 21.0.

Description

Technical Field

[0001] The present disclosure relates to the field of material science, and in particular, to an InP-phthalocyanine composite material and a preparation method thereof. Background Art

[0002] As laser technology is widely used in communications, imaging, information storage, military and other fields, the huge harm caused by laser technology to human organs and important equipment has become increasingly prominent. The research on laser protection materials and devices has also attracted people's attention. As an important optical material, optical limiting materials also play an important role in modern optical technology. The optical limiting ability of existing optical limiting materials is low and often cannot meet the application needs of the laser industry. Phthalocyanine compounds have the characteristics of wide limiting window, obvious limiting effect and rapid response. They are a kind of optical limiting materials with great application prospects. Phthalocyanine compounds have a large electronic conjugated system, and it is easy for intermolecular aggregation to occur through π-π interaction, which reduces the solubility of phthalocyanine molecules and leads to a reduction in the optical limiting effect. Therefore, reducing aggregation is one of the necessary conditions to ensure that phthalocyanine molecules have excellent optical limiting properties.

[0003] The invention provides an InP-phthalocyanine composite material and a preparation method thereof, which can effectively reduce the aggregation between phthalocyanine molecules, and at the same time InP can further improve the optical limiting ability of the material. Summary of the invention

[0004] The purpose of this application is to provide an InP-phthalocyanine composite material and a preparation method thereof, which can solve at least one of the above-mentioned technical problems. The specific solution is as follows:

[0005] In some embodiments, a method for preparing an InP-phthalocyanine composite material is characterized by comprising the following steps:

[0006] S1: Weigh In powder and P powder and put them into quartz boat No. 1;

[0007] S2: Weigh the phthalocyanine and put it into quartz boat No. 2;

[0008] S3: placing the No. 1 quartz boat and the No. 2 quartz boat into a dual-temperature zone tube furnace, and placing substrate materials on the surfaces of the No. 1 quartz boat and the No. 2 quartz boat;

[0009] S4: introducing Ar gas or N2 gas, with the direction of the gas flow being from the No. 1 quartz boat to the No. 2 quartz boat.

[0010] S5: Setting a heating program so that the two temperature zones reach the target temperature at the same time, and the target temperatures of the two temperature zones are the same or different;

[0011] S6: Stop heating and cool naturally to room temperature;

[0012] S7: collecting the composites on the substrate material in the No. 1 quartz boat and the No. 2 quartz boat to obtain the InP-phthalocyanine composite material.

[0013] In some embodiments, the molar ratio of the In powder to the P powder is 1:0.8 to 1:1.5.

[0014] In some embodiments, the molar mass of the In powder is 1 to 100 mmol, the molar mass of the P powder is 1 to 100 mmol, and the molar mass of the phthalocyanine is 1 to 100 mmol.

[0015] In some embodiments, in step S3, the substrate material is at least one of the following:

[0016] Double-polished sapphire, SiO2 / Si wafer or quartz wafer.

[0017] In some embodiments, the flow rate of the Ar gas or the N2 gas is 10-100 sccm.

[0018] In some embodiments, in step S5, setting a heating program so that the two temperature zones reach the target temperature at the same time includes:

[0019] Setting the heating time of the two temperature zones to ensure that the heating rates of the two temperature zones are the same;

[0020] When the target temperatures of the two temperature zones are different, the temperature zone with a higher target temperature is started to be heated first; when the interval values ​​to be heated of the two temperature zones are the same, the temperature zone with a lower target temperature is started to be heated so that the two temperature zones reach the target temperature at the same time;

[0021] When the target temperatures of the two temperature zones are the same, the two temperature zones are started to be heated simultaneously so that the two temperature zones reach the target temperature at the same time.

[0022] In some embodiments, the heating time is 0.5 to 8 hours; the heating rate is 5 to 20° C. / min.

[0023] In some embodiments, the target temperature of the No. 1 quartz boat is 500-700°C, and the target temperature of the No. 2 quartz boat is 400-600°C.

[0024] In some embodiments, the InP-phthalocyanine composite material prepared according to the preparation method is characterized in that the InP-phthalocyanine composite material includes InP having a nano-granular structure; and a phthalocyanine material distributed on the surface and / or inside the nano-granular structure.

[0025] In some embodiments, the InP having a nano-granular structure has a particle size of 50-100 nm.

[0026] Compared with the prior art, the above solution of the embodiment of the present disclosure has at least the following beneficial effects:

[0027] The present application provides a method for preparing an InP-phthalocyanine composite material, comprising the following steps: compounding InP with a nano-granular structure and a phthalocyanine material to obtain an InP-phthalocyanine composite material, which can effectively reduce the aggregation between phthalocyanine molecules, and at the same time, InP improves the light limiting ability of the material. Experiments show that the linear transmittance of the composite material is 80%, and the output amplitude is 0.76 J / cm 2 , the nonlinear limit transmittance is 4.75%, the NAF value is 16.8, and the nonlinear attenuation factor is about 21.0. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The drawings herein are incorporated into the specification and constitute a part of the specification, showing embodiments consistent with the present disclosure, and together with the specification, are used to explain the principles of the present disclosure. Obviously, the drawings described below are only some embodiments of the present disclosure, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work. In the drawings:

[0029] Figure 1 This is a flow chart for the preparation of InP-phthalocyanine composite materials.

[0030] Figure 2 Schematic diagram of a dual temperature zone tubular furnace.

[0031] Figure 3 This is a scanning electron microscope image of the InP-phthalocyanine composite material.

[0032] Figure 4 This is the optical limiting performance curve of InP-phthalocyanine composite material.

[0033] Figure 5 This is the optical limiting performance curve of pure phthalocyanine.

[0034] In the attached drawings: 1-quartz boat No. 1; 2-quartz boat No. 2; 3-dual temperature zone tubular furnace. DETAILED DESCRIPTION

[0035] In order to make the purpose, technical solutions and advantages of the present disclosure clearer, the present disclosure will be further described in detail below in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present disclosure, rather than all of the embodiments. Based on the embodiments in the present disclosure, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present disclosure.

[0036] It should also be noted that the terms "include", "comprises" or any other variations thereof are intended to cover non-exclusive inclusion, so that a product or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such product or device. In the absence of more restrictions, the elements defined by the sentence "comprises a" do not exclude the presence of other identical elements in the product or device including the elements.

[0037] Phthalocyanine compounds have the characteristics of wide limiting window, obvious limiting effect and rapid response, and are a kind of optical limiting material with great application prospects. However, due to the large electron conjugation system, phthalocyanine compounds are prone to intermolecular aggregation through π-π interaction, which reduces the solubility of phthalocyanine molecules and leads to a reduction in the optical limiting effect.

[0038] Based on this, the present application proposes an InP-phthalocyanine composite material and a preparation method thereof, which can effectively reduce the aggregation between phthalocyanine molecules, and at the same time InP can further improve the optical limiting ability of the material.

[0039] The following is combined with Figure 1-4 Detailed description of the optional embodiments of the present application.

[0040] The present application provides a method for preparing an InP-phthalocyanine composite material, such as Figure 1 As shown, the specific steps are:

[0041] S1: Weigh In powder and P powder and put them into quartz boat No. 1;

[0042] S2: Weigh the phthalocyanine and put it into quartz boat No. 2;

[0043] S3: placing the No. 1 quartz boat and the No. 2 quartz boat into a dual-temperature zone tube furnace, and placing substrate materials on the surfaces of the No. 1 quartz boat and the No. 2 quartz boat;

[0044] S4: introducing Ar gas or N2 gas, with the direction of the gas flow being from the No. 1 quartz boat to the No. 2 quartz boat.

[0045] S5: Setting a heating program to ensure that the heating rates of the two temperature zones are the same and the target temperature is reached at the same time;

[0046] S6: Keep warm, stop heating, and cool to room temperature;

[0047] S7: collecting the composites on the substrate material in the No. 1 quartz boat and the No. 2 quartz boat to obtain the InP-phthalocyanine composite material.

[0048] In step S1, the molar ratio of the In powder to the P powder is 1:0.8 to 1:1.5. Since the molar ratio of In and P in the generated substance InP is 1:1, the molar ratio of the two raw materials should be around 1:1. Within this molar ratio range, it is beneficial to synthesize the InP without causing waste of raw materials. It is adjusted according to the actual reaction rate and the participation efficiency of the raw materials.

[0049] Furthermore, the molar mass of the In powder is 1 to 100 mmol, the molar mass of the P powder is 1 to 100 mmol, and the In powder and the P powder are evenly mixed and placed in the No. 1 quartz boat;

[0050] In step S2, the molar mass of the phthalocyanine is 1-100 mmol, which is placed in the No. 2 quartz boat, and the molar mass of the phthalocyanine is adjusted according to the optical limiting effect.

[0051] In step S3, the No. 1 quartz boat and the No. 2 quartz boat are placed in the two temperature zones of the tube furnace respectively, and substrate materials are placed on the surfaces of the No. 1 quartz boat and the No. 2 quartz boat. The substrate material is conducive to the nucleation growth of the raw material. At the same time, this material is relatively inert and will not react with In and P. It can withstand high temperatures and has a clean and smooth surface. In a specific embodiment, the substrate material is at least one of the following:

[0052] Double-polished sapphire, SiO2 Si wafer or quartz wafer.

[0053] In step S4, the Ar gas or N2 gas is used as a carrier gas, the gas flow rate is 10-100 sccm, and the direction of the gas flow is from the No. 1 quartz boat to the No. 2 quartz boat. Figure 2 As shown, it is beneficial to the diffusion of the In powder and the P powder. The carrier gas flow rate is adjusted to blow the In powder and the P powder toward the No. 2 quartz boat for chemical vapor deposition to obtain an InP-phthalocyanine composite material.

[0054] In the present application, the target temperature of the No. 1 quartz boat is 500-700° C., and the target temperature of the No. 2 quartz boat is 400-600° C. In a specific embodiment, the heating procedure includes:

[0055] Setting the heating time of the two temperature zones to ensure that the heating rates of the two temperature zones are the same;

[0056] When the target temperatures of the two temperature zones are different, the temperature zone with a higher target temperature is started to be heated first; when the interval values ​​to be heated of the two temperature zones are the same, the temperature zone with a lower target temperature is started to be heated so that the two temperature zones reach the target temperature at the same time;

[0057] Specifically, the temperature zone of the No. 1 quartz boat is started first, and when the temperature zone of the No. 1 quartz boat has the same value as the zone to be heated of the No. 2 quartz boat, the temperature zone of the No. 2 quartz boat is started to be heated, so that the temperature zones of the No. 1 quartz boat and the No. 2 quartz boat reach the target temperature at the same time; and / or, the temperature zone of the No. 2 quartz boat is started first, and when the temperature zone of the No. 2 quartz boat has the same value as the zone to be heated of the No. 1 quartz boat, the temperature zone of the No. 1 quartz boat is started to be heated, so that the temperature zones of the No. 2 quartz boat and the No. 1 quartz boat reach the target temperature at the same time;

[0058] When the target temperatures of the two temperature zones are the same, heating the two temperature zones is started simultaneously so that the two temperature zones reach the target temperatures at the same time;

[0059] Specifically, when the target temperatures of the temperature zones of quartz boat No. 1 and quartz boat No. 2 are the same, the two temperature zones are heated simultaneously so that the temperature zones of quartz boat No. 1 and quartz boat No. 2 reach the target temperatures at the same time, which is beneficial to the synthesis of InP and the composite of InP and phthalocyanine materials.

[0060] The heating time and the temperature satisfy the following relationship:

[0061]

[0062] Among them, t0 is the initial time, t1 is the final time, T0 is the initial temperature, T2 is the target temperature, v T is the heating rate;

[0063] In some embodiments, the initial time of the No. 1 quartz boat is the same as or different from the initial temperature of the No. 2 quartz boat, and the initial temperature is determined by the target temperature to be reached by the two temperature zones; the final time of the No. 1 quartz boat is the same as the final time of the No. 2 quartz boat; the initial time of the No. 1 quartz boat is the same as the heating rate of the No. 2 quartz boat;

[0064] Further, the heating rate is 5 to 20°C / min;

[0065] Furthermore, the heating time is 0.5 to 8 hours; when the two temperature zones reach the target temperature at the same time, the In powder and the P powder are combined in the No. 1 quartz boat, and then enter the No. 2 quartz boat for chemical vapor precipitation, while keeping the carrier gas flow rate unchanged, to obtain the InP-phthalocyanine composite material.

[0066] Furthermore, after stopping the heating, the carrier gas flow rate is kept unchanged, and after the temperature is naturally cooled to room temperature, the InP-phthalocyanine composite material is taken out. Figure 3 shown.

[0067] According to a specific embodiment of the present disclosure, on the other hand, the present application provides an InP-phthalocyanine composite material prepared by the preparation method described in the above technical solution, including InP having a nano-granular structure;

[0068] and a phthalocyanine material distributed on the surface and / or inside the nano-granular structure.

[0069] Preferably, the nanoparticle size of the InP having a nanoparticle structure is 50-100 nm.

[0070] The InP-phthalocyanine composite material prepared in Example 1 was tested for its optical limiting performance. Figure 4 As shown, Figure 4 This is a test diagram of the optical limiting performance of the InP-phthalocyanine composite material prepared in Example 1 of the present application. Figure 4 It can be seen that when the input energy is low, the output energy is linearly related to the output energy, that is, the InP-phthalocyanine composite material has a linear transmittance. The linear transmittance of the InP-phthalocyanine composite material is 80%, and the output amplitude is 0.76 J / cm 2 ; When the output energy increases continuously and reaches a certain threshold, the output energy is no longer linearly related to the input energy, and the output energy gradually tends to a more stable state. At this time, the transmittance of the InP-phthalocyanine composite material is nonlinear, with a nonlinear limit transmittance of 4.75%, a NAF value of 16.8, and a nonlinear attenuation factor of about 21.0 times. Among them, the linear transmittance is relatively large, which can ensure that as much light as possible is transmitted when the incident light intensity is very weak; the nonlinear transmittance must be relatively small to ensure that as little light as possible is transmitted when strong light is incident, which plays an effective protective role.

[0071] This application tests the optical limiting performance of pure phthalocyanine materials, and the results are as follows Figure 5 As shown, from Figure 5 It can be seen that the linear transmittance of the pure phthalocyanine material is 81%, and the output amplitude is 1.17 J / cm 2The nonlinear limit transmittance is 7.33%, the NAF value is 11, and the nonlinear attenuation ratio is about 13.6 times. Compared with the test results of the light limiting performance of the InP-phthalocyanine composite material, it can be seen that: the output amplitude is the maximum output energy of the material that does not damage the light limiter. The test results show that the output amplitude of the InP-phthalocyanine composite material is smaller than that of the pure phthalocyanine material. The smaller the output amplitude, the better the performance of the light limiting material; the nonlinear limit transmittance of the InP-phthalocyanine composite material is smaller than that of the pure phthalocyanine material, indicating that when strong light is incident, the InP-phthalocyanine composite material can allow less light to pass through, thereby playing an effective protective role; at the same time, the NAF value represents the ratio of linear transmittance to nonlinear transmittance. The larger the NAF value, the stronger the light limiting effect of the material. The test results show that the InP-phthalocyanine composite material has a stronger light limiting effect than the pure phthalocyanine material; the nonlinear attenuation ratio is the reciprocal of the nonlinear limit transmittance. The larger the nonlinear attenuation ratio, the less the material transmits strong light, which plays an effective protective role. The test results show that the nonlinear attenuation rate of the InP-phthalocyanine composite material is greater than the nonlinear attenuation rate of the pure phthalocyanine material, so the InP-phthalocyanine composite material has a more effective protective effect.

[0072] Finally, it should be noted that the various embodiments in this specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the various embodiments can be referred to each other. For the system or device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant parts can be referred to the method part description.

[0073] The above embodiments are only used to illustrate the technical solutions of the present disclosure, rather than to limit them. Although the present disclosure has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present disclosure.

Claims

1. A method for preparing an InP-phthalocyanine composite material, characterized in that: The following steps are involved: S1: Weigh In powder and P powder and put them into quartz boat No. 1; S2: Weigh the phthalocyanine and put it into quartz boat No. 2; S3: placing the No. 1 quartz boat and the No. 2 quartz boat into a dual-temperature zone tube furnace, and placing substrate materials on the surfaces of the No. 1 quartz boat and the No. 2 quartz boat; S4: introducing Ar gas or N2 gas, with the direction of the gas flow being from the No. 1 quartz boat to the No. 2 quartz boat. S5: Setting a heating program so that the two temperature zones reach the target temperature at the same time, and the target temperatures of the two temperature zones are the same or different; S6: Stop heating and cool naturally to room temperature; S7: collecting the composites on the substrate material in the No. 1 quartz boat and the No. 2 quartz boat to obtain the InP-phthalocyanine composite material.

2. The method for preparing the InP-phthalocyanine composite material according to claim 1, characterized in that: In the step S1, the molar ratio of the In powder to the P powder is 1:0.8 to 1:1.

5.

3. The method for preparing the InP-phthalocyanine composite material according to claim 1, characterized in that: The molar mass of the In powder is 1 to 100 mmol, the molar mass of the P powder is 1 to 100 mmol, and the molar mass of the phthalocyanine is 1 to 100 mmol.

4. The method for preparing the InP-phthalocyanine composite material according to claim 1, characterized in that: In step S3, the substrate material is at least one of the following: Double-polished sapphire, SiO2 / Si wafer or quartz wafer.

5. The method for preparing the InP-phthalocyanine composite material according to claim 1, characterized in that: In the step S4, the flow rate of the Ar gas or the N2 gas is 10 to 100 sccm.

6. The method for preparing the InP-phthalocyanine composite material according to claim 1, characterized in that: In step S5, setting a heating program so that the two temperature zones reach the target temperature simultaneously includes: Setting the heating time of the two temperature zones to ensure that the heating rates of the two temperature zones are the same; When the target temperatures of the two temperature zones are different, the temperature zone with a higher target temperature is started to be heated first; when the interval values ​​to be heated of the two temperature zones are the same, the temperature zone with a lower target temperature is started to be heated so that the two temperature zones reach the target temperature at the same time; When the target temperatures of the two temperature zones are the same, the two temperature zones are started to be heated simultaneously so that the two temperature zones reach the target temperature at the same time.

7. The method for preparing the InP-phthalocyanine composite material according to claim 6, characterized in that: The heating time is 0.5 to 8 hours; the heating rate is 5 to 20° C. / min.

8. The method for preparing the InP-phthalocyanine composite material according to claim 1, characterized in that: The target temperature of the No. 1 quartz boat is 500-700°C, and the target temperature of the No. 2 quartz boat is 400-600°C.

9. An InP-phthalocyanine composite material prepared by the preparation method according to any one of claims 1 to 8, characterized in that: The InP-phthalocyanine composite material includes InP having a nano-granular structure; and a phthalocyanine material distributed on the surface and / or inside of the nano-granular structure.

10. The composite material according to claim 9, characterized in that The particle size of the InP with nano-granular structure is 50-100 nm.

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