DEVICE FOR RECEIVING A SOLID SAMPLE MATERIAL AND SYSTEM AND METHOD USING THIS DEVICE

Description

[0001] The present invention relates to a device for receiving and spatially and depth-resolved analysis of a solid sample material, and to a system comprising such a device, a laser device, and optionally a mass spectrometric device. The invention further relates to a method for analyzing a solid sample material using a device according to the invention.

[0002] The increasing use of materials or coatings based on organic compounds in industry (e.g., polymeric materials or paints and varnishes) as well as in many areas of everyday life (e.g., films and packaging materials) requires reliable characterization of the substances used. For questions in areas such as plastics processing, failure analysis, or plastics recycling, information on the chemical composition of solid sample materials is particularly necessary.

[0003] While established and well-known standard methods for organic analysis, such as liquid chromatography or gas chromatography coupled with mass spectrometric detection, provide access to this information, their application is associated with significant disadvantages. The solid sample material must be prepared prior to the actual analysis, i.e., it must be dissolved or dissolved in a volatile or gaseous compound. This entails additional work steps that are not only time-consuming but also represent potential sources of error. Furthermore, information about the exact localization of analytes is lost during sample preparation, so that typically only information about the average composition of the sample material can be obtained. However, a spatially resolved analysis would be useful for many research questions.

[0004] To circumvent the disadvantages associated with sample preparation, methods are known that allow the direct analysis of organic material in solid samples. Examples include infrared spectroscopy and various laser-based organic mass spectrometry methods. Compared to the classical approaches described above, these methods do not require complex sample preparation, thus generally allowing for significantly higher sample throughput.

[0005] However, even the latter methods for the direct analysis of solid sample material are often inadequate, particularly with regard to the available analytes, spatial resolution, and the ability to conduct depth-resolved analyses. However, enabling depth-resolved analysis is an important aspect, as the analytical characterization of sample materials with layered structures has gained massive importance in recent years.

[0006] In contrast to the analysis of organic compounds, different analytical methods are already used in the field of elemental analysis for the investigation of depth profiles. Examples include glow discharge mass spectrometry (GD-MS), secondary ion mass spectrometry (SIMS), or laser-based methods such as Laser Induced Breakdown spectroscopy (LIBS) or laser ablation combined with inductively coupled plasma mass spectrometry (LA-ICP-MS) are examples of such techniques. However, such methods do not allow for the acquisition of compound-specific information.

[0007] Due to its destructive nature, laser-based analysis is well-suited for spatially and depth-resolved analysis with achievable resolutions in the µm range. Laser-material interaction achieves the ablation of solid sample material, which is then transported to the analysis device in the form of extremely fine particles by means of a fluid flow. The spatial and depth resolution depend, among other things, on the laser device used, but the behavior and transport of the ablated solid sample material are also crucial.

[0008] In this regard, the flow rate of the fluid stream is of great importance, which, for example, in the case of LA-ICP-MS, is usually in the range of a few liters per minute. The mass spectrometric devices used for elemental analysis are compatible with such high flow rates. If such a system were coupled with a mass spectrometric device for organic and molecular analysis, the high fluid throughput would not be suitable for analysis with sufficient sensitivity; the flow rate would have to be reduced, which would, however, impair the leaching behavior of the ablated solid sample material and thus reduce the spatial and depth resolution, resulting in a conflict of objectives.

[0009] From WO2014 / 114803 A2 a device according to the preamble of claim 1 is known.

[0010] Further prior art is known from US2013 / 0162991A1, DE 20 2004 005 991 U1 and US 5,308,979.

[0011] It is therefore an object of the present invention to resolve the conflict of objectives described above and to provide a device that can be used for the direct spatially and depth-resolved analysis of solid sample material and that allows the acquisition of molecular information or the use with a mass spectrometric device suitable for organic and molecular analysis.

[0012] In particular, the device according to the invention should therefore be suitable for use with a mass spectrometric device using electron impact ionization under vacuum conditions, since particularly valuable molecular information can be obtained with such a mass spectrometric approach. However, the device according to the invention can be used with another suitable form of ionization.

[0013] These and other objects are achieved by a device having the features of the independent patent claim.

[0014] The present invention relates to a device for receiving and analyzing a solid sample material, in particular for laser-based chemical analysis, comprising a substantially gas-tight housing with a sample receiving area arranged within the housing, wherein the housing comprises a window permeable to a laser beam, wherein the device has an inlet device for introducing a fluid flow to the sample receiving area and a first outlet device and a second outlet device for diverting the fluid flow charged with ablated sample material from the sample receiving area.

[0015] According to the invention, the outlet devices are designed such that the outgoing volume flows of the fluid flow are in a ratio of between 100:1 and 5000:1, in particular between 500:1 and 2000:1, between the first outlet device and the second outlet device.

[0016] Within the scope of the present invention, it was discovered that the use of two outlet devices and the division of the fluid flow allow high volume flows to be directed through the sample receiving area while still enabling analysis of the solid sample material ablated by the laser beam in a mass spectrometric device for organic analysis. On the one hand, the high volume flows at the inlet side allow for good washout of ablated solid sample material from the sample receiving area. On the other hand, the fluid flow containing sample material exiting the second outlet device can be analyzed in a mass spectrometric device that is only suitable for introducing low volume flows.

[0017] In one specific embodiment, the fluid stream is a gas stream, preferably a helium stream. Depending on the application, however, other gases or mixtures of two or more gases can also be used. The use of a liquid is also possible.

[0018] Optionally, it is provided that the inlet device is designed to introduce a fluid stream, in particular a gas, preferably helium, into the sample receiving area at a flow rate between 0.5 L / min and 5 L / min, in particular between 0.5 L / min and 2 L / min. Optionally, these flow rates occur at a pressure between 0.5 bar and 2 bar. Preferred flow rates are between 0.8 L / min and 2.0 L / min, in particular between 1.2 L / min and 1.8 L / min. These fluid parameters enable particularly good washout behavior. In particular, the sample receiving area can have an internal volume of less than or equal to 5 cm3, in particular less than or equal to 2 cm2, preferably less than or equal to 1 cm3.

[0019] Optionally, the housing may have an inlet opening to which the inlet device is connected, a first outlet opening to which the first outlet device is connected, and a second outlet opening to which the second outlet device is connected. The arrangement of inlet and outlet openings in the housing enables a particularly efficient division of the fluid flow.

[0020] Optionally, it is provided that a main flow direction of the fluid flow runs between the inlet opening and the first outlet opening, and that the second outlet opening is arranged at an angle α between 10° and 90°, in particular between 30° and 60°, with respect to the main flow direction. In particular, the first outlet opening can be arranged exactly opposite the inlet opening. The main part of the fluid flow then flows through the sample receiving area in a substantially linear manner, and the smaller volume flow, which is diverted to the second outlet opening, flows away from the main flow direction at an angle α.

[0021] If appropriate, the sample collection area may be circular or drop-shaped. This allows for good washout behavior that is similar across the entire sample collection area.

[0022] Optionally, it is provided that the first outlet device has a length L 1 and a flow cross-section Q 1 , and that the second outlet device has a length L 2 and a flow cross-section Q 2 . Optionally, the outlet devices each comprise outlet hoses with the stated length and the stated flow cross-section.

[0023] The lengths of the outlet devices extend, in particular, from the respective outlet opening in the housing to an outlet end of the outlet device. In particular, the end of the second outlet device can be connectable to a mass spectrometric device. Optionally, the end of the first outlet device can also be connectable to an analytical device, in particular to a mass spectrometric device or to an emission spectroscopic device.

[0024] The lengths L 1 and L 2 thus specifically indicate the distance through which a fluid flow can or does flow in the respective outlet device. If the flow cross-section is not constant over the entire length of the outlet device, the aforementioned flow cross-sections can each indicate the smallest flow cross-section along the length of an outlet device.

[0025] If appropriate, the volume flow (V 2 ) exiting the second outlet device is defined by the length (L 2 ) and the cross-sectional area (Q 2 ) of the second outlet device. In particular, this also determines the division ratio of the total volume flow (V 0 ) supplied via the inlet device.

[0026] This volume flow can be described by the Hagen-Poissuille law, which according to equation 1 is: V 2 = πr 4 Δ p 8 η l

[0027] Where: V 2 ... volume flow exiting the second outlet device; r... Radius of the second outlet device; Δ p ...pressure drop across the second outlet device (= initial pressure minus final pressure); η...dynamic viscosity of the fluid; ℓ...length of the second outlet device.

[0028] The division ratio V 1 / V 2 of the gas flow supplied via the inlet device results from the two volume flows V 1 and V 2 according to equation 2: V 1 = V 0 − V 2

[0029] In particular, assuming a sufficiently large outlet for the volume flow V 1, the length and flow cross-section of the second outlet determine the pressure drop on this side. This allows the ratio of the partial volume flows exiting both outlets to be determined.

[0030] If appropriate, it is therefore provided that the first outlet device has essentially no pressure drop, in particular for volume flows of less than 2 L / min, wherein the fluid is preferably a gas, particularly preferably helium. "Essentially no pressure drop" means, in particular, that the final pressure is less than 1% below the initial pressure.

[0031] Preferably, the housing has no further outlet openings from which the fluid can escape, apart from the first outlet opening and the second outlet opening. Therefore, apart from the inlet opening and the two outlet openings, the housing can be designed to be substantially fluid-tight, in particular gas-tight.

[0032] Where appropriate, the flow cross-section Q 2 is between 0.003 and 0.12 mm 2<.

[0033] Where appropriate, the inlet device may include an inlet hose.

[0034] Optionally, the housing is arranged on a movement device configured to move the housing translationally, in particular in three directions arranged essentially orthogonally to one another. This allows the position of the solid sample material to be changed relative to the laser beam to enable ablation at different locations on the sample material.

[0035] Optionally, the second outlet device may comprise a heating device configured to heat the second outlet device at least in sections. In particular, the heating device may also be configured to heat fluid located in the second outlet device and any removed sample material contained therein. This can reduce the risk of condensation of removed sample material inside the second outlet device. It has been found that using the heating device can improve the washout behavior of the device and thus also the peak shape of the mass spectrometric signals.

[0036] Optionally, it is provided that the heating device is designed to heat the second outlet device at least in sections to a temperature of at least 70°C, in particular at least 100°C.

[0037] The heating device can, for example, be designed as a heating jacket that at least partially surrounds the second outlet device.

[0038] The invention further relates to a system comprising a device according to the invention, as well as a laser device, wherein the laser device is configured to emit a laser beam onto a solid sample material arranged in the sample receiving area.

[0039] Optionally, the window has a transmittance of at least 80%, preferably at least 90%, for the wavelength of the laser beam. In particular, the window may comprise or consist of quartz glass or transparent corundum, such as sapphire glass.

[0040] Optionally, the laser device is configured to emit a pulsed monochromatic laser beam with a wavelength of less than 300 nm, and / or the laser device is configured to emit a focused laser beam with a minimum beam diameter of less than 500 µm, in particular less than 200 µm. The laser device can, in particular, be configured to emit a laser beam with a wavelength of approximately 248 nm, 224 nm, 213 nm, or 193 nm. The laser device can comprise a solid-state laser or a gas-phase laser.

[0041] Optionally, the system further comprises a mass spectrometric device, wherein the mass spectrometric device is configured to ionize sample material in the fluid stream ablated by the laser beam by electron impact ionization in a vacuum. The mass spectrometric device is connected to the second outlet device for receiving the fluid stream or is connectable thereto. Optionally, the mass spectrometric device can alternatively or additionally be configured to ionize sample material in the fluid stream ablated by the laser beam by another suitable form of ionization in a vacuum.

[0042] Optionally, the outlet end of the second outlet device is connected to or connectable to a sample introduction opening of the mass spectrometric device.

[0043] Optionally, the mass spectrometric device comprises an ion source configured for ionizing the sample material, wherein the ion source comprises an electrode arrangement for generating an electric field. Optionally, the electrode arrangement comprises a cathode and an anode, and the potential difference is adjustable within a range between 10 V and 100 V. Optionally, the ion source comprises a heating device configured, in particular, to provide a temperature between 100°C and 300°C in the ion source. Optionally, the mass spectrometric device comprises a pumping device configured to provide a pressure of less than 10 -4 Pa, in particular less than 10 -5 Pa, in the ion source.

[0044] Optionally, an observation device is provided for visually observing the sample receiving area through the window, wherein the laser beam is preferably guided or can be guided through an optical system of the observation device.

[0045] Optionally, the observation device may comprise an emission analysis device configured to analyze emission radiation generated during the interaction of the laser beam with a solid sample material. For this purpose, the observation device may, for example, comprise an emission radiation collection device and a spectroscopic unit, the latter being configured to analyze the radiation collected by the emission radiation collection device.

[0046] Optionally, the system further comprises an analysis device connected to the first outlet device. The analysis device can be configured to subject sample material in the fluid stream, which has been removed by the laser beam, to a chemical analysis. The analysis device can be, for example, a further mass spectrometric device, but also, for example, an emission spectroscopic device. Preferably, the analysis device comprises an inductively coupled plasma into which the gas stream emerging from the first outlet device can be introduced. In this case, the further analysis can be carried out by means of mass spectrometric detection and / or by means of emission spectrometric detection. Optionally, the analysis device is suitable for determining elemental information from the solid sample material.

[0047] The invention further relates to a method for analyzing a solid sample material using a device according to the invention. The method may comprise the following steps: Placing the sample material in the sample receiving area, ablating sample material by means of a laser device, transporting the ablated sample material with a fluid flow flowing from the inlet device via the sample receiving area to the first outlet device and to the second outlet device, wherein the exiting volume flows of the fluid flow are in a ratio between 100:1 and 5000:1, in particular between 500:1 and 2000:1, between the first outlet device and the second outlet device, analyzing the ablated sample material exiting the second outlet device together with the fluid flow with a mass spectrometric device which is configured to ionize the sample material by electron impact ionization in a vacuum.

[0048] Optionally, the mass spectrometric device may alternatively or additionally be configured to ionize ablated sample material by another suitable form of ionization in a vacuum.

[0049] Where appropriate, it is provided that the volume flow of the fluid flowing through the inlet device is between 0.5 L / min and 5 L / min, in particular between 0.5 L / min and 2 L / min, where appropriate at a pressure between 0.5 bar and 2 bar.

[0050] Optionally, it is provided that the volume flow of the fluid flow exiting through the second outlet device is less than 10 mL / min, in particular less than 5 mL / min, preferably between 0.25 and 2.5 mL / min.

[0051] Further features of the present invention emerge from the patent claims, the figures and the description of the embodiment.

[0052] The present invention is explained in detail below using exemplary embodiments.

[0053] They show: Fig. 1 a schematic perspective view of a device according to the invention according to a first embodiment; Fig. 2 a schematic view of a system comprising a device according to the invention according to the first embodiment; Fig. 3 an exemplary mass spectrum of polymethyl methacrylate; and Fig. 4 an exemplary mass spectrum of polystyrene.

[0054] Fig. 1 A schematic perspective view of a device according to the invention according to a first exemplary embodiment. The device comprises a housing 1 with a sample receiving area arranged therein, which in this example is circular in plan view. The housing 1 is formed by a cover 16 and a housing base 22, wherein the cover 16 is connected to the housing base 22 via screws 18. The cover 16 comprises a window 3 that is permeable to laser radiation. In this exemplary embodiment, the window is made of quartz glass.

[0055] The housing has three openings: an inlet opening 7, a first outlet opening 8, and a second outlet opening 9. Apart from these three openings, the housing 1 is gas-tight to the environment. An annular seal 17 is provided between the window 3 and the housing base 22 for sealing.

[0056] At the inlet opening 7, an inlet device 4 is arranged, which comprises a connector 23 and an inlet hose 19. At the first outlet opening 8, a first outlet device 5 is arranged, which comprises a connector 23 and a first outlet hose 20. At the second outlet opening 9, a second outlet device 9 is arranged, which comprises a connector 23 and a second outlet hose 21.

[0057] The inlet opening 7 and the first outlet opening 8 are arranged opposite each other. This means that the two openings 7, 8 are arranged along the main flow direction 10 of the gas flow. The second outlet opening 9 is arranged laterally offset from the first outlet opening 8, with the angle α with respect to the main flow direction 10 being approximately 30° in this example.

[0058] If a gas stream is introduced into the sample receiving area 2 via the inlet device 4, it can only flow out of the sample receiving area 2 via the two outlet devices 5, 6. The outlet devices 5, 6 are designed such that the volume flow flowing out via the first outlet device 5 and the second outlet device 6 is in a ratio of approximately 1000 to 1. This means that when a volume flow of approximately 1000 mL / min is introduced via the inlet device 4, approximately 1 mL / min exits the second outlet device 6. The remaining gas flow exits via the first outlet device 5.

[0059] In the present embodiment, this division of the volume flows is determined by appropriately selecting the length and flow cross-section of the outlet devices 5, 6. The length of the outlet devices 5, 6 is the distance traveled by a gas between the beginning and the end of the respective outlet device 5, 6.

[0060] The first outlet device 5 has a length L 1 of approximately 100 cm and a flow cross-section Q 1 of approximately 7 mm 2 . The second outlet device 6 has a length L 2 of approximately 220 cm and a flow cross-section Q 2 of approximately 0.008 mm 2 . If the diameter of the first outlet device 5 is sufficiently large, the volume flow in the second outlet direction 6 is essentially determined only by the length (L 2 ) and the cross-sectional area (Q 2 ) of this second outlet device 6. By controlling the volume flow V 0 supplied to the sample receiving area 2 via the inlet device 4, the division ratio can be controlled over a wide range (approximately 1:100 - 1:5000).

[0061] Depending on the specific requirements, this ratio can be varied within certain limits. For example, if the length L 2 is reduced, this has a directly proportional effect on Q 2, increasing the ratio and thus also the volume flow exiting the second outlet device 6.

[0062] Fig. 2 shows a schematic view of a system comprising the device according to the invention according to the first embodiment. The system also includes a laser device 11 and a mass spectrometric device 13.

[0063] The inlet device 4 is connected to a gas container 24 in order to be able to introduce gas into the sample receiving area 2.

[0064] In this embodiment, the laser device 11 comprises a pulsed nanosecond solid-state laser. The laser device 11 generates a laser beam 12 with a wavelength of 266 nm. The laser beam 12 is guided through the window 3, which is made of quartz glass, into the sample receiving area 2. The optical manipulation of the laser beam 12 takes place in the observation device 14, which also includes a microscope system for observing the sample receiving area 2. This arrangement allows the section of the sample receiving area 2 to which the laser beam 12 is directed to be observed at all times.

[0065] The optical system of the observation device 14 allows the cross-section of the laser beam 12 to be adjusted in the sample receiving area 2 or at the surface of the solid sample material (not shown). In this embodiment, the cross-section is variably adjustable between 10 µm and 200 µm.

[0066] In this system, the housing 1 of the device according to the invention is arranged on a movement device 15, which is designed as a motorized stage and can move the housing 1 translationally in three spatial directions. This allows the relative position between the solid sample material and the laser beam 12 to be adjusted.

[0067] In the system shown here, the first outlet device 5 opens into a fume hood (not shown), where the escaping gas is fed for cleaning and disposal. The gas that also escapes from the first outlet device 5 is therefore not reused. In one example, however, that gas could also be fed for further analysis. For example, the end of the first outlet device 5 could be connected to another mass spectrometric device, such as an ICP-MS device. Alternatively, the end of the first outlet device 5 could be connected to another analytical device, for example an emission spectroscopic device, such as an ICP-OES device. By connecting the first outlet device 5 to another analytical device, information about the elemental composition of the solid sample material can also be obtained, for example.

[0068] The second outlet device 6 opens into the mass spectrometric device 13, which is designed as a device using electron impact ionization under vacuum conditions. The mass spectrometric device 13 comprises an ionization chamber, to which the end of the second outlet device 6 is connected and into which the exiting gas stream flows. The features of such a device are well known in the art and will not be explained in detail here. The mass spectrometric device 13 can utilize another suitable form of ionization as an alternative to or in addition to electron impact ionization.

[0069] The analysis of a solid sample material with a system of Fig. 2 can be carried out as follows: The solid sample material is placed in the sample receiving area 2 of the device, the housing 1 is closed and flushed with gas from the gas container 24, which flows into the sample receiving area 2 via the inlet device 4 at approximately 1000 mL / min. Due to the described division of the volume flows, approximately 1 mL / min of this gas flow exits the second outlet device 6 and flows into the mass spectrometric device 13. The remainder of the gas flow exits through the first outlet device 5.

[0070] A position on the surface of the solid sample material intended for analysis is then selected via the observation device 14, and the laser beam 12 is focused on this position; the selected position is irradiated with the laser beam 12. The introduced energy causes ablation of the sample material, which means that solid sample material is transferred into the gas space in the form of particles and gaseous products. The ablation cloud generated locally at the position of laser ablation is transported by the gas flow to the outlet devices 5, 6, and a portion of the ablated sample material passes through the second outlet device 6 to the mass spectrometric device 13, where the analysis of the solid sample material, or more precisely, the aerosol of the solid sample material, takes place.

[0071] With the system from Fig. 2 The mass spectra obtained are shown as examples in the Fig. 3 und 4 shown. In the Fig. 3 und 4 In the diagrams shown, m / z values ​​are plotted on the x-axis, while the y-axis shows relative intensity values. m / z values ​​indicate the mass-to-charge ratio of detected ions.

[0072] Fig. 3 shows a mass spectrum obtained during the analysis of polymethyl methacrylate as a solid sample material. Electron impact ionization in the mass spectrometric device 13 generates fragment ions that are characteristic of the analyzed sample material. Examples of characteristic fragment ions in Fig. 3 have m / z values ​​of 41, 55, 69 and 100.

[0073] Fig. 4 shows a mass spectrum obtained during the analysis of polystyrene as a solid sample material. Electron impact ionization in the mass spectrometric device 13 generates fragment ions that are characteristic of the analyzed sample material. Examples of characteristic fragment ions in Fig. 4 have m / z values ​​51, 78, 91 and 102, 104 and 117.

[0074] The characteristic fragment ions can be used, for example, to identify the solid sample material, for example by comparing it with reference tables or databases.

[0075] Within the scope of the present invention, the system of Fig. 2 Variations are also made with regard to the gas flow flowing through the inlet device 4. Fig. 5 shows the relationship between the intensity of the total ion current (TIC) during ablation of a polymethyl methacrylate sample and the width of the resulting peak. The intensity is an important parameter with regard to the sensitivity of the analysis, while the peak width reflects the washout behavior of the device. Fig. 5 It can be seen that the ratio reaches a maximum at approximately 1200 mL / min. This means that the device exhibits the greatest performance at this gas flow.

[0076] Furthermore, a two-layer sample with an upper layer of polyimide and a lower layer of polymethyl methacrylate was tested with the system of Fig. 2 The point of incidence of the laser beam 12 or the laser pattern was not changed during this analysis, which allowed a depth profile of the sample material to be obtained. The intensity curves of the peaks at m / z values ​​51, 74, and 98 (representative of polyimide) and 41, 69, and 100 (representative of polymethyl methacrylate) are shown in Fig. 6 It is clearly visible that the polyimide signal decreases with increasing number of laser shots, while the polymethyl methacrylate signal increases, reflecting the layered sample structure.

[0077] Fig. 7 shows a further embodiment of a system according to the invention. Fig. 7 The system presented here largely corresponds to the one already described in Fig. 2 In contrast to the system from Fig. 2 the system indicates Fig. 7 At the second outlet device 6, a heating device 25 is provided, which is designed as a heating jacket surrounding the second outlet device 6. By using the heating device 25, the peak shape of the mass spectrometric signals can be improved.

[0078] Since the system consists of Fig. 7 in the further technical features with the system from Fig. 2 corresponds, please refer to the description of this figure. Bezugszeichenliste

[0079] 1 Housing 2 Sample receiving area 3 Window 4 Inlet device 5 First outlet device 6 Second outlet device 7 Inlet opening 8 First outlet opening 9 Second outlet opening 10 Main flow direction 11 Laser device 12 Laser beam 13 Mass spectrometric device 14 Observation device 15 Movement device 16 Cover 17 Seal 18 Fastening screw 19 Inlet hose 20 First outlet hose 21 Second outlet hose 22 Housing base 23 Connector 24 Gas container 25 Heating device

Claims

1. An apparatus for accommodating and for analysing a solid sample material in a spatially and depth-resolved manner, in particular for laser-based chemical analysis, comprising a substantially gas-tight sealed housing (1) with a sample-accommodating region (2) arranged inside the housing (1), wherein the housing (1) comprises a window (3) that is transparent to a laser beam, wherein the apparatus has an inlet device (4) for introducing a fluid flow into the sample-accommodating region (2) and a first outlet device (5) and a second outlet device (6) for discharging the fluid flow loaded with ablated sample material from the sample-accommodating region (2),characterised in that the outlet devices (5, 6) are formed in such a way that the ratio between the volume flows of the fluid flow exiting from the first outlet device (5) and of the fluid flow exiting from the second outlet device (6) is between 100:1 and 5000:1, in particular between 500:1 and 2000:1.

2. The apparatus according to claim 1, characterised in that the inlet device (4) is configured to introduce a fluid flow, in particular a gas, preferably helium, at a flow rate of between 0.5 L / min and 5 L / min, in particular between 0.5 L / min and 2 L / min.

3. The apparatus according to claim 1 or 2, characterised in that the housing (1) has an inlet opening (7) to which the inlet device (4) is connected, in that the housing (1) has a first outlet opening (8) to which the first outlet device (5) is connected, and in that the housing (1) has a second outlet opening (9) to which the second outlet device (6) is connected.

4. The apparatus according to claim 3, characterised in that a main flow direction (10) of the fluid flow runs between the inlet opening (7) and the first outlet opening (8), and in that the second outlet opening (9) is arranged at an angle α between 10 ° and 90 °, in particular between 30 ° and 60 °, in relation to the main flow direction (10).

5. The apparatus according to any one of claims 1 to 4, characterised in that the sample-accommodating region (2) is circular or drop-shaped.

6. The apparatus according to any one of claims 1 to 5, characterised in that the first outlet device (5) has a length L1 and a flow cross-section Q1, wherein the length L1 and a flow cross-section Q1 are selected such that the first outlet device (5) has substantially no pressure drop, and in that the second outlet device (6) has a length L2 and a flow cross-section Q2 wherein optionally the flow cross-section Q2 is between 0.003 and 0.12 mm2.

7. The apparatus according to any one of claims 1 to 6, characterised in that the housing (1) is arranged on a movement device (15) which is configured to translationally move the housing (1), in particular in three directions which are substantially orthogonal to one another.

8. The apparatus according to any one of claims 1 to 7, characterised in that the second outlet device (6) comprises a heating device (25) which is configured to heat the second outlet device (6) at least sectionally, wherein the heating device (25) is optionally configured to heat the second outlet device (6) at least sectionally to a temperature of at least 70 °C.

9. A system comprising an apparatus according to any one of claims 1 to 8 and a laser apparatus (11), wherein the laser apparatus (11) is configured to emit a laser beam (12) onto a solid sample material placed in the sample-accommodating region (2).

10. The system according to claim 9, characterised in that the window (3) has a transmittance of at least 80%, preferably at least 90%, for the wavelength of the laser beam (12).

11. The system according to claim 9 or 10, characterised in that the laser apparatus (11) is configured to emit a pulsed monochromatic laser beam (12) with a wavelength of less than 300 nm, and / or in that the laser apparatus (11) is configured to emit a focused laser beam (12) with a minimum beam diameter of less than 500 µm, in particular less than 200 µm.

12. The system according to any one of claims 9 to 11, further comprising - a mass spectrometric apparatus (13), wherein the mass spectrometric apparatus (13) is configured to ionise sample material in the fluid flow ablated by means of the laser beam (12) by electron impact ionisation and / or by another form of ionisation in a vacuum, wherein the mass spectrometric apparatus (13) is connected to the second outlet device (6) for accommodating the fluid flow. and / or - an analysis apparatus, wherein the analysis apparatus is configured to chemically analyse the sample material in the fluid flow ablated by the laser beam (12), wherein the analysis apparatus is connected to the first outlet device (5) for accommodating the fluid flow.

13. The system according to any one of claims 9 to 12, characterised in that an observation apparatus (14) is provided for visual observation of the sample-accommodating region (2) through the window (3), wherein the laser beam (12) is preferably guidable or is guided through an optical system of the observation apparatus (14), wherein the observation apparatus (14) optionally comprises an emission analysis apparatus configured to analyse emission radiation generated upon interaction of the laser beam (12) with a solid sample material.

14. A method for spatially and depth-resolved analysis of a solid sample material with an apparatus according to any one of claims 1 to 8, comprising the following steps: - Placing the sample material in the sample-accommodating region (2), - Ablating the sample material by means of a laser apparatus (11), - Transporting the ablated sample material with a fluid flow flowing from the inlet device (4) via the sample-accommodating region (2) to the first outlet device (5) and to the second outlet device (6), wherein the exiting volume flows of the fluid flow are in a ratio of between 100:1 and 5000:1, in particular between 500:1 and 2000:1, between the first outlet device (5) and the second outlet device (6), - Analysing the ablated sample material exiting together with the fluid flow from the second outlet device (6) with a mass spectrometric apparatus (13) which is configured to ionise the sample material by electron impact ionisation and / or by another form of ionisation in a vacuum.

15. The method according to claim 14, characterised in that the volume flow of the fluid flow flowing in through the inlet device (4) is between 0.5 L / min and 5 L / min, in particular between 0.5 L / min and 2 L / min, at a pressure of between 0.5 bar and 2 bar, and / or in that the volume flow of the fluid flow exiting through the second outlet device (6) is less than 10 mL / min.