Let's suppose we have an isotropic homogeneous dielectric $D$ (with given relative constant $\epsilon_r$) surrounded by the void.
Inside and outside $D$ we can obviously write the Poisson equations:
$\nabla^2 V=\frac{\rho}{\epsilon_0\epsilon_r}$ (inside $D$), $\quad$ $\nabla^2 V=\frac{\rho}{\epsilon_0}$ (outside $D$).
Here $\rho$ simply represents a limited free charge distribution in the space (inside and/or outside $D$, but not on the boundary $\partial D$ of $D$).
On the boundary $\partial D$ (which separates the void and the dielectric) obviously we cannot write the Poisson equation. However on $\partial D$ we obviously have the conditions:
$\hat{n} \cdot (\vec{E}_1-\epsilon_r\vec{E}_2)=0, \quad \hat{n} \times (\vec{E}_1-\vec{E}_2)=0$,
where $\hat{n}$ is the versor normal to the surface $\partial D$, while $\vec{E}_1$ and $\vec{E}_2$ are respectively the electric fields outside and inside $D$.
We moreover impose the Dirichlet boundary condition at infinity such that $V=0$.
My question
Are those conditions enough to say that there exists a unique solution $V$?
i.e. we solve $\nabla^2 V=\frac{\rho}{\epsilon_0}$ outside $D$ (with boundary condition $V=0$ at infinity) obtaining the (non unique) solution $V_1$ ($V_1$ is not unique because we have not given the value of $V$ over the boundary $\partial D$, so the uniqueness theorem does not apply);
then we solve $\nabla^2 V=\frac{\rho}{\epsilon_0\epsilon_r}$ inside $D$ obtaining the (non unique) solution $V_2$;
then we connect the two (non unique) solutions through the conditions $\hat{n} \cdot (\vec{E}_1-\epsilon_r\vec{E}_2)=0$ and $\hat{n} \times (\vec{E}_1-\vec{E}_2)=0$ on the boundary $\partial D$, obtaining the total solution $V$.
Is this total solution $V$ unique?
An example of the procedure I used can be found here (page 12, example 2): https://unlcms.unl.edu/cas/physics/tsymbal/teaching/EM-913/section4-Electrostatics.pdf