Laser dye solution with wide laser spectrum output range and preparation method thereof

Abstract

The invention relates to a laser dye solution with a wider laser spectrum output range and a preparation method thereof, belongs to the technical field of laser dyes, and solves the problem that the tunable laser spectrum output range of the laser dye in the prior art is narrower. The laser dye solution comprises a donor dye rhodamine 610, an acceptor dye rhodamine 101 and a solvent. The laser output range of the mixed laser dye containing rhodamine 610 and rhodamine 101 in a dye laser is obviously improved compared with that of a single dye.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of laser dyes, in particular to a laser dye solution with a wide laser spectrum output range and a preparation method thereof. BACKGROUND

[0002] Since the advent of laser, it has been widely studied in various fields due to its excellent monochromatic performance. Tunable laser can output laser of various wavelengths according to requirements, and the core material thereof is a tunable laser medium with a wide band energy level structure. Among various tunable lasers, dye laser is the most mature and most studied tunable laser device.

[0003] Laser dye is the core gain medium for dye laser, and in the dye laser, laser dye can be excited by an excitation light source to generate tunable laser of different wavelengths. Limited by the radiation transition mechanism of dye molecules and the limited stokes shift, the high-efficiency tunable laser wavelength range of a single laser dye in the prior art is usually only about 20 nm, and the efficiency is low at the edge wavelength, and the tunable spectrum range is narrow. For example, the effective laser output range of the classic laser dye rhodamine 610 is usually 580 nm-600 nm. When carrying out spectral scanning by using a dye laser, the laser spectrum line needs to be as wide as possible to realize wide-band laser scanning.

[0004] In the prior art, when laser scanning in a wide band is needed, dye solution needs to be frequently replaced to realize dye laser output in a larger range. The wavelength required for some isotope excitation ionization is often not in the high-efficiency laser output band of the dye, and it is difficult to find a suitable laser dye for laser output. SUMMARY

[0005] In view of the above analysis, the embodiments of the present application aim to provide a laser dye solution with a wide laser spectrum output range and a preparation method thereof, so as to solve the problem of narrow tunable laser spectrum output range of the existing laser dye.

[0006] In one aspect, the present application provides a laser dye solution with a wide laser spectrum output range, which comprises a donor dye rhodamine 610, an acceptor dye rhodamine 101 and a solvent.

[0007] Preferably, the molar ratio of the donor dye rhodamine 610 to the acceptor dye rhodamine 101 is 10:1-10:4.

[0008] Preferably, the concentration of the donor dye rhodamine 610 is 2x10 -4 -6x10 -4The concentration of the acceptor dye rhodamine 101 is calculated according to the molar ratio of the donor dye rhodamine 610 to the acceptor dye rhodamine 101.

[0009] Preferably, the solvent is a mixture of alcohol and water.

[0010] Preferably, the solvent is a mixture of ethanol and water, or a mixture of propanol and water.

[0011] In a second aspect, the present application further provides a preparation method of the laser dye solution, which comprises the following steps: (1) dissolving the donor dye rhodamine 610 in alcohol, and then adding water to obtain a rhodamine 610 dye solution; (2) dissolving the acceptor dye rhodamine 101 in alcohol, and then adding water to obtain a rhodamine 101 dye solution; (3) mixing the rhodamine 610 dye solution and the rhodamine 101 dye solution to obtain a laser dye solution.

[0012] Preferably, in step (1), the amount of alcohol is 20-80% of the total amount of alcohol in the solvent, and the amount of water is 20-80% of the total amount of water in the solvent.

[0013] Preferably, in step (2), the amount of alcohol is 20-80% of the total amount of alcohol in the solvent, and the amount of water is 20-80% of the total amount of water in the solvent.

[0014] In a third aspect, the present application further provides a dye laser, which comprises the laser dye solution.

[0015] Preferably, the laser spectrum output range of the dye laser is 591-629 nm.

[0016] Compared with the prior art, the present application can achieve at least one of the following beneficial effects: 1. When using a single dye solution in a dye laser, the laser output wavelength range of Rhodamine 610 (Rh610) dye solution is approximately 580nm-600nm, and effective laser output is only possible within a laser spectrum range of approximately 20nm; the laser output wavelength range of Rhodamine 101 (Rh101) dye solution is approximately 605nm-626nm, and effective laser output is only possible within a laser spectrum range of approximately 21nm. This invention mixes Rh610 and Rh101 dyes. Both Rh610 and Rh101 are Rhodamine-type dyes and do not chemically react, allowing for effective mixing. By appropriately adjusting the ratio of the two dyes, in a preferred embodiment, the mixed dye solution can achieve effective laser output in the 591nm-629nm wavelength range, with a tunable laser spectrum width reaching 38nm, far exceeding that of a single Rh610 or Rh101 dye.

[0017] 2. This invention uses a mixed solvent solution of organic solvent and water, which avoids the high safety risks such as flammability, explosiveness and toxicity caused by using only organic reagents to dissolve dyes in the prior art.

[0018] 3. The mixed laser dye solution in this invention is simple to prepare, and the laser output range of the mixed laser dye in the dye laser is significantly improved compared with that of the single dye.

[0019] In this invention, the above-described technical solutions can be combined with each other to achieve more preferred combinations. Other features and advantages of this invention will be set forth in the following description, and some advantages may become apparent from the description or be learned by practicing the invention. The objects and other advantages of this invention can be realized and obtained from what is particularly pointed out in the description and drawings. Attached Figure Description

[0020] The accompanying drawings are for illustrative purposes only and are not intended to limit the invention. Throughout the drawings, the same reference numerals denote the same parts.

[0021] Figure 1 The molecular structure of the Rh610 dye molecule; Figure 2 The molecular structure of the Rh101 dye molecule; Figure 3 The absorption spectra are those of the mixed dye Rh610+Rh101 in Example 1 and the single dyes Rh610 and Rh101 in Comparative Examples 1-2. Figure 4 The fluorescence spectra of the mixed dye Rh610+Rh101 in Example 1 and the single dyes Rh610 and Rh101 in Comparative Examples 1-2 are shown. Figure 5 Laser tuning curve of single dye Rh610, Rh101 of Comparative Example 3 in a dye laser; Figure 6 Laser tuning curve of different Rh610 and Rh101 mixing ratio of Example 2 in a dye laser; Figure 7 Laser tuning curve of Rh610 and Rh101 of Comparative Example 5 in a dye laser when the molar ratio is low; Figure 8 Laser tuning curve of Rh610 and Rh101 of Comparative Example 6 in a dye laser when the molar ratio is high; Figure 9 Laser tuning curve of Rh610 and Rh101 of Comparative Example 7 in a dye laser when the concentration of Rh610 is low in the mixed dye solution; Figure 10 Laser tuning curve of Rh610 and Rh101 of Comparative Example 8 in a dye laser when the concentration of Rh610 is high in the mixed dye solution. DETAILED DESCRIPTION

[0022] The preferred embodiments of the present application will be described in detail below with reference to the drawings, which form a part of this application. The drawings illustrate embodiments of the application and, together with the description, serve to explain the principles of the application, and are not intended to limit the scope of the application.

[0023] The present application provides a laser dye solution with a wider laser spectrum output range, which comprises a donor dye rhodamine 610, an acceptor dye rhodamine 101 and a solvent.

[0024] Compared with the prior art, the present application mixes two dyes, Rh610 and Rh101, both of which are rhodamine dyes and can be effectively mixed without chemical reaction, thereby widening the laser spectrum output range. In a preferred embodiment, by adjusting the molar ratio of Rh610 and Rh101, the mixed dye solution can effectively output laser in the wavelength range of 591 nm-629 nm, and the width of the tunable laser spectrum reaches 38 nm, which is much wider than that of single Rh610 or Rh101.

[0025] The principle of the mixed solution of Rh610 and Rh101 widening the laser spectrum output range is that two different dye molecules, the donor dye rhodamine 610 and the acceptor dye rhodamine 101, have the molecular structures as shown in Figure 1 and Figure 2 When D absorbs excitation light and is in an excited state D*, if A exists nearby, the excitation energy of D* is transferred to the nearby A, and A is in an excited state A*, which will emit fluorescence, and the process is shown in formula (1): Formula (1), where h is Planck's constant and v is the frequency of the emitted photon.

[0026] This phenomenon is called fluorescence resonance energy transfer or FRET. For resonance energy transfer to occur, the following conditions must be met: both D and A must be able to fluoresce, ensuring that both dyes can effectively absorb and emit photons; the emission spectrum of D and the excitation (or absorption) spectrum of A must overlap partially; and the distance between D and A must be less than 10 nm.

[0027] Formula (2), where R0 is the critical transfer distance, k 2 is an orientation factor, usually taken as the constant 2 / 3, ψ D is the fluorescence quantum yield of the donor dye, n is the refractive index of the solution, and N is Avogadro's number. The integral term represents the overlap integral of the donor emission spectrum and the acceptor absorption spectrum as a function of photon frequency v.

[0028] The critical energy transfer distance R0 is the distance between dye molecules at which the rate of resonance transfer is equal to the rate of self-deactivation of the donor, also known as the Forster distance. The Forster distance indicates that the efficiency of energy transfer between a donor molecule and an acceptor molecule decreases as the sixth power of the distance between them. Therefore, the ability of a donor fluorophore to transfer its excitation energy to an acceptor through non-radiative interactions decreases sharply with increasing distance between the molecules, thus limiting the phenomenon of resonance energy transfer to a maximum donor-acceptor separation radius of approximately 10 nm. When the donor and acceptor radii are equal to the Forster distance, the transfer efficiency is 50%. At this separation radius, half of the donor excitation energy is transferred to the acceptor through resonance energy transfer, while the other half is dissipated through the combination of all other available processes, including fluorescence emission. Theoretically, the Forster critical distance is the maximum separation length between a donor and an acceptor molecule at which resonance energy transfer still occurs.

[0029] The critical energy transfer distance R0 determines the rate of energy transfer from the donor to the acceptor. The greater the critical energy transfer distance R0, the greater the rate of resonance energy transfer; conversely, the smaller the critical energy transfer distance R0, the smaller the rate of resonance transfer. If the critical energy transfer distance is 0, it means that there is no overlap between the donor fluorescence spectrum and the acceptor absorption spectrum, and there will be no energy transfer.

[0030] R0 is essentially a reflection of the overlap of the emission and absorption spectra of the two molecules, with a larger value indicating better overlap. For two specified dye molecules in a particular solution, R0 is fixed. From Figure 3 and Figure 4The spectrum can be seen that two dyes, the emission spectrum of Rh610 overlaps with the absorption spectrum of Rh101 more, so the combination of the two can expand the laser spectrum output range.

[0031] Exemplarily, the molar ratio of the donor dye Rhodamine 610 to the acceptor dye Rhodamine 101 is 10:1-10:4, for example, 10:1, 10:2, 10:3, 10:4. The molar ratio of the two within the range can better reflect the laser broadening phenomenon.

[0032] Exemplarily, the concentration of the donor dye Rhodamine 610 is 2×10 -4 -6×10 -4 mol / L, for example, 2×10 - 4 mol / L, 3×10 -4 mol / L, 4×10 -4 mol / L, 5×10 -4 mol / L, 6×10 -4 mol / L. If the concentration of Rhodamine 610 is too low, the gain is not enough, and the dye laser cannot be output, and if the concentration of Rhodamine 610 is too high, concentration quenching will occur, and the laser performance will also be greatly reduced. The concentration of the acceptor dye Rhodamine 101 is calculated according to the molar ratio of the donor dye Rhodamine 610 to the acceptor dye Rhodamine 101.

[0033] Exemplarily, the solvent is a mixture of alcohol and water.

[0034] Exemplarily, the volume ratio of alcohol to water is 1:1.

[0035] Exemplarily, the solvent is a mixture of ethanol and water, or a mixture of propanol and water.

[0036] In a second aspect, the present application also provides a preparation method of the above laser dye solution, which comprises the following steps: (1) dissolving the donor dye Rhodamine 610 in alcohol, and then adding water to obtain a Rhodamine 610 dye solution; (2) dissolving the acceptor dye Rhodamine 101 in alcohol, and then adding water to obtain a Rhodamine 101 dye solution; (3) mixing the Rhodamine 610 dye solution and the Rhodamine 101 dye solution to obtain a laser dye solution.

[0037] The amount of alcohol and water used in steps (1) and (2) can only dissolve the two dyes on the premise of meeting the final solution concentration.

[0038] Exemplarily, in step (1), the amount of alcohol is 20-80% of the total amount of alcohol in the solvent, and the amount of water is 20-80% of the total amount of water in the solvent.

[0039] Exemplarily, in step (2), the amount of alcohol is 20-80% of the total amount of alcohol in the solvent, and the amount of water is 20-80% of the total amount of water in the solvent.

[0040] In a third aspect, the present application further provides a dye laser, which comprises the above-mentioned laser dye solution.

[0041] Exemplarily, the laser spectrum output range of the dye laser is 591-629 nm.

[0042] Hereinafter, the laser dye solution with a wider laser spectrum output range and the preparation method thereof of the present application will be further illustrated by specific examples.

[0043] Example 1 This example is used to illustrate the absorption spectrum and fluorescence spectrum of the mixed dye Rh610+Rh101. Since the ultraviolet-visible spectrophotometer and the fluorescence spectrometer are not suitable for testing high-concentration dye solutions, this example uses a low-concentration dye solution.

[0044] Preparation of dye solution: a mixed dye solution with a total concentration of 1×10 -5 mol / L of Rh610 and Rh101 is prepared, the molar ratio of Rh610 to Rh101 is 10:1, and the solvent is ethanol and water, and the volume ratio of ethanol to water is 1:1.

[0045] Comparative Example 1 This comparative example is similar to the dye solution of Example 1, except that the solution does not contain Rh101, and the concentration of Rh610 is 1×10 -5 mol / L.

[0046] Comparative Example 2 This comparative example is similar to the dye solution of Example 1, except that the solution does not contain Rh610, and the concentration of Rh101 is 1×10 -5 mol / L.

[0047] The absorption spectrum and fluorescence spectrum of the dye solutions of Example 1 and Comparative Examples 1-2 are detected, and the detection method is to test the absorption and emission spectrum of the dye solution in the ultraviolet-visible spectrophotometer and the fluorescence spectrometer, respectively, by using a four-way quartz colorimetric cell with a thickness of 10 mm, and the results are shown in Figure 3 and Figure 4 . Figure 3are the absorption spectra of single dye Rh610, Rh101 and mixed dye Rh610+Rh101, it can be seen that the absorption spectrum of the mixed dye solution covers most of the range of the absorption spectra of the two single dyes, and the mixed dye solution has a wider absorption spectrum; Figure 4 are the fluorescence spectra of single dye Rh610, Rh101 and mixed dye Rh610+Rh101, it can be seen that the fluorescence spectrum of the mixed dye solution is broadened, and its fluorescence output range is more like a certain degree of superposition of the two dyes, indicating that the mixed dye solution has a wider fluorescence output peak, and the wide fluorescence output range also indicates a wider laser output range of the mixed dye solution to a certain extent.

[0048] Example 2 This example is used to illustrate that the Rh610 dye and the Rh101 dye with different molar ratios form laser dye solutions with a wider laser spectrum output range in a mixed solvent of ethanol and water.

[0049] The preparation method comprises the following steps: (1) 4×10 -4 mol of Rh610 dye is weighed into a beaker, 300 ml of ethanol solution is injected, and the solution is stirred and dissolved by a magnetic stirrer, and then 300 ml of pure water is injected to obtain a Rh610 dye solution; (2) 4×10 -5 mol, 8×10 -5 mol, 12×10 -5 mol, and 16×10 -5 mol of Rh101 dye is weighed into a beaker respectively, 200 ml of ethanol solution is injected respectively, and the solution is stirred and dissolved by a magnetic stirrer, and then 200 ml of pure water is injected respectively to obtain Rh101 dye solutions with different concentrations; (3) The above Rh610 dye solution is mixed with the Rh101 dye solutions with different concentrations respectively, and after being uniformly mixed, laser dye solutions with a molar ratio of Rh610 dye and Rh101 dye of 10:1, 10:2, 10:3, and 10:4 and a concentration of Rh610 of 4×10 -4 mol / L are obtained.

[0050] Example 3 This example is used to illustrate that the Rh610 dye and the Rh101 dye with different molar ratios form laser dye solutions with a wider laser spectrum output range in a mixed solvent of n-propanol and water.

[0051] The preparation method comprises the following steps: (1) 4×10 -4mol Rh610 dye, placed in a beaker, injected with 300 ml of n-propanol solution, dissolved by magnetic stirrer, then injected with 300 ml of pure water, to obtain Rh610 dye solution; (2) Respectively take 4×10 -5 mol, 8×10 -5 mol, 12×10 -5 mol, 16×10 -5 mol Rh101 dye, respectively placed in a beaker, respectively injected with 200 ml of n-propanol solution, dissolved by magnetic stirrer, then respectively injected with 200 ml of pure water, to obtain Rh101 dye solution of different concentrations; (3) The above Rh610 dye solution is mixed with Rh101 dye solution of different concentrations, and after mixing, laser dye solutions with Rh610 and Rh101 molar ratio of 10:1, 10:2, 10:3, 10:4 and Rh610 concentration of 4×10 -4 mol / L are obtained.

[0052] Comparative Example 3 This comparative example provides a laser dye solution similar to Example 2, except that it does not contain Rh101 dye, and the concentration of Rh610 dye is 4×10 -4 mol / L.

[0053] Comparative Example 4 This comparative example provides a laser dye solution similar to Example 2, except that it does not contain Rh610 dye, and the concentration of Rh101 dye is 4×10 -4 mol / L.

[0054] The laser dye solutions of Example 2 and Comparative Examples 3-4 are applied to a dye laser, and the laser tuning curve is detected. The detection method is as follows: the laser dye solutions of Example 2 and Comparative Examples 3-4 are respectively applied to a dye laser, in the dye laser, 532 nm laser is used as a laser pump source, the dye laser cavity assembly is adjusted, every 1 nm a group of laser output wavelength and corresponding output probability are tested, the laser output wavelength is read out by a wavelength meter, and the output power is read out by a laser power meter, and the results are shown in Figures 5-6 .

[0055] Figure 5 is the laser tuning curve of single dye Rh610 and Rh101 in a dye laser, Figure 6 is the laser tuning curve of different Rh610 and Rh101 mixing ratio in a dye laser, from Figure 5 and Figure 6It can be seen that the tunable laser spectrum range of the laser dye solution containing both Rh610 and Rh101 is much wider than that of the single Rh610 dye or Rh101 dye, and the tunable laser spectrum range is the widest when the molar ratio of Rh610 to Rh101 is 10:2, which is 38 nm.

[0056] Comparative Example 5 This comparative example provides a laser dye solution similar to Example 2, except that the concentration of Rh610 dye in the laser dye solution is 4x10 -4 mol / L, and the molar ratio of Rh610 to Rh101 is 10:0.5.

[0057] The laser dye solution of this comparative example is applied to a dye laser, and the results are shown in Table 5. Figure 7 It can be seen that when the molar ratio of Rh610 to Rh101 is 10:0.5, the tunable laser spectrum range of the mixed dye (581 nm-606 nm) is significantly lower than that of the mixed dye solution with a molar ratio of 10:1 (592 nm-628 nm), and is closer to that of the Rh610 dye solution itself.

[0058] Comparative Example 6 This comparative example provides a laser dye solution similar to Example 2, except that the molar ratio of Rh610 to Rh101 in the laser dye solution is 10:5.

[0059] The laser dye solution of this comparative example is applied to a dye laser, and the results are shown in Table 6. Figure 8 It can be seen that when the molar ratio of Rh610 to Rh101 is 10:5, the tunable laser spectrum range of the mixed dye (601 nm-636 nm) is very similar to that of the mixed dye solution with a molar ratio of 10:4 (600 nm-635 nm), and increasing the content of Rh101 has limited effect on increasing the broadening range when the molar ratio of Rh610 to Rh101 is 10:4.

[0060] Comparative Example 7 This comparative example provides a laser dye solution similar to Example 2, except that the molar ratio of Rh610 to Rh101 in the laser dye solution is 10:1, and the concentration of Rh610 is 1x10 -4 mol / L.

[0061] The laser dye solution of this comparative example is applied to a dye laser, and the results are shown in Table 7. Figure 9 It can be seen that at this time, the broadening range of the mixed dye is 588 nm-615 nm, and the maximum output power of the laser is about 1.2 W, which is less than that of the Rh610 dye solution with a concentration of 2x10 -4The data of the laser dye solution of the comparative example 8 is shown in Table 2.

[0062] Comparative Example 8 The comparative example 8 provides a laser dye solution similar to the example 2, except that the molar ratio of Rh610 and Rh101 in the laser dye solution is 10:1, and the concentration of Rh610 is 7 x 10 -4 mol / L.

[0063] The laser dye solution of the comparative example 8 is applied to a dye laser, and the results are shown in Table 2. Figure 10 It can be seen that the mixed dye broadens the range of 595 nm-628 nm, and both the dye broadening range and the output power are less than the data when the concentration of Rh610 is 6 x 10 - 4 mol / L.

[0064] From the comparison of the comparative examples and the examples, it can be seen that when the molar ratio of Rh610 and Rh101 is in the preferred range of 10:1-10:4 of the present application, and the concentration of Rh610 is 2 x 10 -4 - 6 x 10 -4 mol / L, the tunable laser spectrum range is larger.

[0065] The above description is only the preferred specific implementation of the present application, but the protection scope of the present application is not limited to this. Any change or replacement within the technical range disclosed by the present application can be easily thought by those skilled in the art, and should be covered in the protection scope of the present application.

Claims

1. A laser dye solution having a wider range of laser spectral output, characterized in that, The laser dye solution comprises a donor dye rhodamine 610, an acceptor dye rhodamine 101 and a solvent.

2. The laser dye solution of claim 1, wherein, The molar ratio of the donor dye rhodamine 610 to the acceptor dye rhodamine 101 is 10:1-10:

4.

3. The laser dye solution of claim 2, wherein, The concentration of the donor dye Rhodamine 610 is 2 x 10 -4 -6 x 10 -4 -2, and the concentration of the acceptor dye Rhodamine 101 is calculated according to the molar ratio of the donor dye Rhodamine 610 to the acceptor dye Rhodamine 101.

4. The laser dye solution of claim 1, wherein, The solvent is a mixture of alcohol and water.

5. The laser dye solution of claim 4, wherein, The solvent is a mixture of ethanol and water, or a mixture of propanol and water.

6. The method of claim 1-5, wherein the laser dye solution is prepared by the steps of: The preparation method comprises the following steps: (1) dissolving the donor dye rhodamine 610 in alcohol, and then adding water to obtain a rhodamine 610 dye solution; (2) dissolving the acceptor dye rhodamine 101 in alcohol, and then adding water to obtain a rhodamine 101 dye solution; (3) mixing the rhodamine 610 dye solution and the rhodamine 101 dye solution to obtain a laser dye solution.

7. The production method according to claim 6, wherein In step (1), the amount of alcohol is 20-80% of the total amount of alcohol in the solvent, and the amount of water is 20-80% of the total amount of water in the solvent.

8. The preparation method according to claim 6, characterized in that, In step (2), the amount of alcohol is 20-80% of the total amount of alcohol in the solvent, and the amount of water is 20-80% of the total amount of water in the solvent.

9. A dye laser, characterized by comprising: The dye laser comprises the laser dye solution according to any one of claims 1-5.

10. The dye laser of claim 9, wherein, The laser spectrum output range of the dye laser is 591-629 nm.

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